Early applications of encapsulated acetamides for reduced injury in crops

ABSTRACT

Methods of reducing injury to crop foliage and achieving weed control using encapsulated acetamide herbicides in pre-plant or preemergence crop plant applications are described. A composition comprising a first population of a particulate microencapsulated acetamide herbicide and a second population of a particulate microencapsulated acetamide herbicide is described wherein the application mixture exhibits a bimodal acetamide release profile. The compositions provide reduced crop injury through controlled herbicide release.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/497,565, filed Mar. 22, 2012, which is the U.S. National StageApplication based on International Application Serial No.PCT/US2011/048303, filed Aug. 18, 2011, which claims the benefit of U.S.Provisional Application Ser. No. 61/374,984, filed Aug. 18, 2010, andU.S. Provisional Application Ser. No. 61/375,029, filed Aug. 18, 2010,the entire contents of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to methods of reducing injury tocrop foliage and achieving commercial weed control using encapsulatedacetamide (e.g., encapsulated acetanilide) herbicides. In particular,the present invention provides encapsulated acetamide (e.g.,encapsulated acetanilide) herbicide compositions and methods that enableapplication preemergence to crop plants whereby simultaneouscommercially acceptable weed control and commercially acceptable cropinjury can be attained.

BACKGROUND OF THE INVENTION

The emergence of glyphosate-resistant weeds has generated interest inthe use of residual herbicides as tank-mix partners with glyphosate inglyphosate-tolerant (e.g., ROUNDUP READY or RR) crops. Acetamideherbicides, including, for example, acetanilide herbicides, typically donot offer significant post-emergence activity, but as a residual partnerwould provide control of newly emerging monocots and small-seeded dicotweed species. This would usefully supplement the activity of glyphosatewhich is effective on emerged weeds, but lacks significant residualactivity.

Commercially available acetanilide herbicide formulations are typicallyapplied after the emergence of the crop (i.e., post-emergent to thecrop), but before the emergence of later germinating weeds (i.e.,preemergent to the weeds). Application during this time window, however,may cause unexpected foliar injury to the crop. Moreover, applicationduring this window has prevented the use of acetanilide herbicides forburndown prior to crop plant emergence. Crop plant injury has beenobserved with both commercially available conventional acetanilideemulsifiable concentrate (EC) formulations and with commerciallyavailable encapsulated acetanilide formulations.

Prior art microencapsulation procedures are generally adequate forproducing formulations with good weed control. However, the practitionerof this art has had some difficulty optimizing the release rates toobtain acceptable bioefficacy for a given active while minimizing cropinjury to commercially acceptable levels. In particular, commercialencapsulated formulations may show greater systemic crop plant injuryover time in the form of leaf crinkling and plant stunting when comparedto emulsifiable concentrates.

In microencapsulation technology known in the art, core herbicide istypically released from a microcapsule at least in part by moleculardiffusion through the shell wall. Modification of shell wall thicknessto increase or decrease herbicide rate has definite limitations.

Thin shell walls are sensitive to premature mechanical rupture duringhandling or in the field, resulting in immediate release. Poor packagestability resulting from shell wall defects can also arise when the corematerial is in direct contact with the external vehicle. As a result,some core material may crystallize outside the capsule causing problemsin spray applications, such as spray nozzle plugging. Further, highershear encountered in certain application means, such as sprayapplications, can result in shell wall rupture and herbicide release.The microcapsule thus becomes little more than an emulsion stabilizedagainst coalescence. When delivered to the field, herbicide release isso fast that little crop safety improvement is gained over conventionalemulsion concentrate formulations.

If the wall thickness is increased, the bioefficacy quickly drops to amarginal performance level because herbicide release is delayed. Thereis also a practical limit to the wall thickness in interfacialpolymerization. As the polymer precipitates, the reaction becomesdiffusion controlled. The reaction rate can drop to such an extent thatnon-constructive side reactions can predominate.

Various formulation solutions have been attempted to address the releaserate limitations. For example, two package or single package blends ofmicrocapsules and dispersions or emulsions of free agricultural activeshave been proposed in Scher, U.S. Pat. Nos. 5,223,477 and 5,049,182.Seitz et al., U.S. Pat. No. 5,925,595 and U.S. Publication No.2004/0137031 A1, teach methods for producing microencapsulatedacetochlor. The degree of permeability is regulated by a compositionalchange in the precursors for the wall. Although the Seitz compositionshave proven effective for weed control, unacceptable crop injury hasbeen observed in connection with the use of those compositions whenapplied to certain commercially important crops.

A need therefore exists for herbicide compositions and methods utilizingacetamide herbicides such as acetanilide herbicides whereby simultaneouscommercially acceptable weed control and commercially acceptable cropinjury can be attained. A further need exists for acetamide (e.g.,acetanilide) herbicide compositions and methods that enable applicationpreemergence to crop plants.

SUMMARY OF THE INVENTION

Among the various aspects of the present invention may be noted theprovision of encapsulated acetamide herbicide compositions and methodsfor use thereof. The present invention provides for acetamideapplication prior to planting of the crop plant or preemergence to thecrop plant wherein herbicide release rate is controlled in order to giveboth commercially acceptable weed control and commercially acceptablecrop injury.

In accordance with one embodiment, the present invention provides amethod for controlling weeds in a field of crop plants. The methodcomprises applying an application mixture to the field in anherbicidally effective amount, wherein the application mixture comprisesat least one particulate microencapsulated acetamide herbicide and theapplication mixture is applied to the field (i) prior to planting of thecrop plant or (ii) preemergence to the crop plant.

In accordance with another embodiment, the present invention provides aparticulate microencapsulated acetamide herbicide composition. Thecomposition comprises a first population of a particulatemicroencapsulated acetamide herbicide and a second population of theparticulate microencapsulated acetamide herbicide. The first and thesecond populations of the particulate microencapsulated acetamideherbicide each comprise a water-immiscible core material comprising theacetamide herbicide and a microcapsule containing the core material andhaving a shell wall comprising a polyurea. The shell wall is formed in apolymerization medium by a polymerization reaction between apolyisocyanate component comprising a polyisocyanate or mixture ofpolyisocyanates and a polyamine component comprising a polyamine ormixture of polyamines to form the polyurea. The first population of theparticulate microencapsulated acetamide herbicide has a mean particlesize of from about 3 μm to 11 μm and the second population of theparticulate microencapsulated acetamide herbicide has a mean particlesize of between 11 μm and about 20 μm. In accordance with one particularembodiment, the composition exhibits a multi-modal acetamide herbiciderelease profile.

Aqueous mixtures comprising the particulate microencapsulated acetamideherbicide compositions in the form of a concentrate or diluted sprayapplication mixture and comprising one or more co-herbicides are alsoprovided.

Other objects and features will be in part apparent and in part pointedout hereinafter.

DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION

In accordance with the present invention, compositions comprisingencapsulated herbicides (e.g., particulate microencapsulated herbicides)having a low initial release rate and a sustained long term release, andmethods for using such compositions, are provided that provide bothcommercially acceptable weed control and commercially acceptable cropinjury. The compositions are useful for the control of weeds whenapplied in a herbicidally effective amount prior to planting of the cropplant or preemergence to the crop plant.

In accordance with the present invention, it has been discovered thatparticulate microencapsulated acetamide (e.g., encapsulated acetanilide)herbicides can be applied to a field before crops are planted or fromplanting up to, but not including, plant emergence in order to achievecommercially acceptable rates of weed control and commerciallyacceptable rates of crop plant emergence and injury. Pre-plant,preemergence acetamide herbicide application in accordance with thepresent invention increases the application window beyond post-emergencein order to provide the benefit of treating a field prior to weedgermination thereby aiding the establishment of crop plants. Inparticular, early application of encapsulated acetanilide herbicide,such as 1-40 days prior to planting, enables acetanilide exposure toweeds at germination in order to provide control of newly emergingmonocots and small seeded dicot species during the early growing seasonwhen the crop plant is more susceptible to competition for water,sunlight and nutrients.

It has been further discovered that, for a given acetamide herbicide,the combination of a first population of a particulate microencapsulatedacetamide herbicide and a second population of a particulatemicroencapsulated acetamide herbicide, wherein the first and secondmicroencapsulated acetamide herbicides have different average size andshell thickness, can provide a longer duration of weed control andreduced crop injury as compared to either population ofmicroencapsulated acetamide herbicide applied individually. Thecombination provides a multi-modal (e.g. bimodal) release profilewherein early acetamide release provides initial weed control withoutsignificant crop injury and sustained release over time providesextended residual control.

As used herein, “prior to planting of the crop plant” refers, forexample, to a time period of from about 40 days prior to planting of thecrop plant to immediately before planting of the crop plant, from about35 days prior to planting of the crop plant to immediately beforeplanting of the crop plant, from about 30 days prior to planting of thecrop plant to immediately before planting of the crop plant, from about25 days prior to planting of the crop plant to immediately beforeplanting of the crop plant, from about 20 days prior to planting of thecrop plant to immediately before planting of the crop plant, from about15 days prior to planting of the crop plant to immediately beforeplanting of the crop plant, from about 10 days prior to planting of thecrop plant to immediately before planting of the crop plant, or fromabout 5 days prior to planting of the crop plant to immediately beforeplanting of the crop plant. “Preemergence to the crop plant” refers toanytime during the interval from planting of the crop plant up to, butnot including, emergence of the crop plant (i.e., before cracking). Forexample, during the interval of from about 1 day after planting, fromabout 2 days after planting, from about 3 days after planting, fromabout 4 days after planting, from about 5 days after planting, fromabout 10 days after planting, from about 15 days after planting, or fromabout 20 days after planting of the crop plant up to, but not including,emergence of the crop plant.

As further used herein, “weed control” refers to any observable measureof control of plant growth, which can include one or more of the actionsof (1) killing, (2) inhibiting growth, reproduction or proliferation,and (3) removing, destroying, or otherwise diminishing the occurrenceand activity of plants. Weed control can be measured by any of thevarious methods known in the art. For example, weed control can bedetermined as a percentage as compared to untreated plants following astandard procedure wherein a visual assessment of plant mortality andgrowth reduction is made by one skilled in the art specially trained tomake such assessments. In another control measurement method, control isdefined as a mean plant weight reduction percentage between treated anduntreated plants. In yet another control measurement method, control canbe defined as the percentage of plants that fail to emerge following apreemergence herbicide application. A “commercially acceptable rate ofweed control” varies with the weed species, degree of infestation,environmental conditions, and the associated crop plant. Typically,commercially effective weed control is defined as the destruction (orinhibition) of at least about 60%, 65%, 70%, 75%, 80%, or even at least85%, or even at least 90%. Although it is generally preferable from acommercial viewpoint that 80-85% or more of the weeds be destroyed,commercially acceptable weed control can occur at much lower destructionor inhibition levels, particularly with some very noxious,herbicide-resistant plants. Advantageously, the herbicidal microcapsulesused in accordance with the present invention achieve commerciallyacceptable weed control in the time period of from application of theherbicide microcapsules, for example as contained in an applicationmixture, to 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9weeks, 10 weeks, 11 weeks, or even 12 weeks after application of theherbicide microcapsules.

Crop damage can be measured by any means known in the art, such as thosedescribed above for weed control determination. A “commerciallyacceptable rate of crop injury” for the present invention likewisevaries with the crop plant species. Typically, a commercially acceptablerate of crop injury is defined less than about 20%, 15%, 10% or evenless than about 5%. The herbicidal microcapsules and methods of thepresent invention limit crop injury to a commercially acceptable rate asmeasured from about 24 hours (about 1 Day After Treatment or DAT) afterapplication to two weeks (about 14 DAT), from about 24 hours (about 1DAT) after application to three weeks (about 21 DAT), or from about 24hours (about 1 DAT) to about four weeks (about 28 DAT).

Acetanilide herbicides within the scope of the present invention areclassified as seedling growth inhibitors. Seedling growth inhibitors areabsorbed and translocated in plants from germination to emergenceprimarily by subsurface emerging shoots and/or seedling roots. Ingeneral, seedling growth inhibitors retard plant cell division throughinterference with lipid and protein synthesis (acetanilides) or celldivision (dinitroanilides) thereby inhibiting shoot elongation andlateral root formation. In dicots (e.g., broadleaf plants), an embryonicshoot comprising three main parts emerges from the seed: the cotyledons(seed leaves), the section of shoot below the cotyledons (hypocotyl),and the section of shoot above the cotyledons (epicotyl). Dicot seedlinggrowth inhibitors are believed to absorb primarily by the hypocotyl andepicotyl. In monocots (e.g., grasses), a coleophile emerges from theseed and extends to the soil surface where elongation terminates andleaves emerge. Monocot seedling growth inhibitors are believed to absorbprimarily by the coleophile.

In contrast to preemergent plants, emergent plants are typicallyrelatively unaffected by seedling growth inhibitor herbicides. For thatreason, prior art practice has been to apply seedling growth inhibitorherbicides after crop emergence, but before weed emergence.

Certain crop plants such as corn, soybean, cotton, peanut and sugarbeets are less susceptible to the action of acetamide herbicides thanare weeds. In accordance with the present invention and based onexperimental evidence to date, it is believed that the controlledacetamide release rate from the microencapsulated acetamide herbicidesin combination with crop plants having reduced acetamide susceptibilityenables commercial control of weeds and commercially acceptable rates ofcrop damage when microencapsulated acetamide herbicides are applied to afield either pre-planting or preemergent to the crop plant. Thiscritical discovery enables the use of seedling growth inhibitoracetamide herbicides, or optionally seedling growth inhibitor acetamideherbicides in combination with one or more co-herbicides, in crop plantpre-planting and preemergence applications, such as for burndown.

In some embodiments of the present invention, crop plants include, forexample, corn, peanuts, potatoes, soybeans, canola, alfalfa, sugarcane,sugarbeets, peanuts, grain sorghum (milo), field beans, rice,sunflowers, wheat and cotton. Crop plants include hybrids, inbreds, andtransgenic or genetically modified plants having specific traits orcombinations of traits including, without limitation, herbicidetolerance (e.g., resistance to glyphosate, glufosinate, dicamba,sethoxydim, etc.), Bacillus thuringiensis (Bt), high oil, high lysine,high starch, nutritional density, and drought resistance. In someembodiments, the crop plants are resistant to organophosphorusherbicides, acetolactate synthase (ALS) or acetohydroxy acid synthase(AHAS) inhibitor herbicides, synthetic auxin herbicides and/or acetylCoA carboxylase (ACCase) inhibitor herbicides, In other embodiments thecrop plants are resistant to glyphosate, dicamba, 2,4-D, MCPA,quizalofop, glufosinate and/or diclofop-methyl. In other embodiments,the crop plant is glyphosate and/or dicamba resistant. In someembodiments of the present invention, crop plants are glyphosate and/orglufosinate resistant. In some other embodiments, the crop plants areglyphosate, glufosinate and dicamba tolerant. Preferred crops includecorn, cotton, soybeans, peanuts and sugarbeets. Particularly preferredcrop species are corn, cotton and soybean.

Acetamide herbicides suitable for the practice of the present inventioninclude dimethenamid, napropamide, pronamide and acetanilide herbicidessuch as acetochlor, alachlor, butachlor, butenachlor, delachlor,diethatyl, dimethachlor, mefenacet, metazochlor, metolachlor,pretilachlor, propachlor, propisochlor, prynachlor, terbuchlor,thenylchlor and xylachlor, mixtures thereof and stereoisomers thereof.Some acetamide herbicides are available in their free forms, as salts,or as derivatized materials, for example, as esters. Any form of theherbicides described herein by name is potentially applicable. Forinstance, the present invention has utility for both racemic metolachlorand S-metolachlor, and racemic dimethenamid and dimethenamid-P.Preferred acetamide herbicides include dimethenamid and dimethenamid-Pand preferred acetanilide herbicides include acetochlor, metolachlor andS-metolachlor.

An additional aspect of the present invention is the use of theencapsulated acetamide formulations as tank mix partners with foliaractive herbicides. An example of a foliar active herbicide includes, butis not limited to, glyphosate. It is well known in the art that themixing of foliar active herbicides with co-herbicides (such asacetamides) and/or other materials which cause foliar injury can, insome cases, result in antagonism wherein the uptake of the foliarherbicides is reduced thereby resulting in lower herbicidaleffectiveness. It is believed that the release rate of the encapsulatedacetamides of the present invention is reduced as compared to prior artcompositions thereby minimizing antagonism such that the co-herbicide(e.g. glyphosate) is effectively absorbed and translocated within theplant before leaf damage induced by the acetamide herbicide cansignificantly interfere with absorption and translocation of theco-herbicide. Therefore, in addition to reducing foliar injury on cropplants, the encapsulated acetamide herbicides of this invention shouldminimize the initial localized foliar injury to previously emerged weedsand thereby allow the foliar active components of the co-herbicide toeffectively and efficiently absorb into and translocate through thepreviously emerged weeds in order to achieve maximum activity in theabsence of antagonism between the acetamide and co-herbicide.

In general, the encapsulated herbicides of the present invention areprepared by contacting an aqueous continuous phase containing apolyamine component comprising a polyamine source and a discontinuousoil phase containing the herbicide and a polyisocyanate componentcomprising a polyisocyanate source. A shell wall is formed in apolymerization reaction between the polyamine source and the isocyanatesource at the oil/water interface thereby forming a capsule ormicrocapsule containing the herbicide. The polyamine source can be amixture of a principal polyamine and one or more auxiliary polyamines,also termed a polyamine mixture. In some embodiments of the presentinvention, the polyamine source consists essentially of a principalpolyamine. As used herein, a principal polyamine (also referred to as aprincipal amine) refers to a polyamine consisting essentially of asingle polyamine species. The polyisocyanate source can be apolyisocyanate or mixture of polyisocyanates.

In accordance with the present invention and based on experimentalevidence, it has been discovered that the objects of the invention canbe achieved by encapsulating herbicides, in particular, acetamides, inmicrocapsules prepared by the selection of one or more certaincompositional and process variables including the molar ratio ofpolyamine to polyisocyanate, the shell wall composition, the weightratio of core material (herbicide component) to shell wall material, thecore material components, the mean microcapsule particle size, processconditions such as mixing shear and time, and combinations thereof.Through the careful selection of these and other factors, aqueousdispersions of microencapsulated herbicides have been developedaccording to the compositions and methods described herein which, ascompared to compositions and methods known in the art, reduce cropfoliage injury for preemergent application to the crop plants to acommercially acceptable level while simultaneously achievingcommercially acceptable weed control for preemergent application to theweeds. Improved crop safety of the present invention is achieved even inthe absence of a safener.

The microcapsule shell of the present invention may preferably comprisea polyurea polymer formed by a reaction between a principal polyamine,and optionally an auxiliary polyamine, having two or more amino groupsper molecule and at least one polyisocyanate having two or moreisocyanate groups per molecule. Release of the herbicide core materialis controlled by the microcapsule shell wall, preferably without theneed for mechanical release (microcapsule rupture).

In some embodiments, the microcapsules may be prepared by encapsulatingcore material in a shell wall formed by reacting polyamine component anda polyisocyanate component in a reaction medium in concentrations suchthat the reaction medium comprises a molar equivalent excess of aminegroups compared to the isocyanate groups. More particularly, the molarconcentration of amine groups from the principal polyamine and optionalauxiliary polyamine and the molar concentration of isocyanate groupsfrom the at least one polyisocyanate (i.e., one polyisocyanate, a blendof two polyisocyanates, a blend of three polyisocyanates, etc.) in thereaction medium is such that the ratio of the concentration of aminemolar equivalents to the concentration of isocyanate molar equivalentsis at least 1.1:1. The molar ratio of concentration of amine molarequivalents to concentration of isocyanate molar equivalents may becalculated according to the following equation:

$\begin{matrix}{{{Molar}\mspace{14mu}{Equivalents}\mspace{14mu}{Ratio}} = \frac{{amine}\mspace{14mu}{molar}\mspace{14mu}{equivalents}}{{polyisocyanate}\mspace{14mu}{molar}\mspace{14mu}{equivalents}}} & (1)\end{matrix}$In the above equation (1), the amine molar equivalents is calculatedaccording to the following equation:amine molar equivalents=Σ([polyamine]/equivalent weight).In the above equation (1), the isocyanate molar equivalents iscalculated according to the following equation:i. isocyanate molar equivalents=Σ([polyisocyanate]/equivalent weight)wherein the polyamine concentration and the polyisocyanate concentrationrefer to the concentration of each in the reaction medium and are eachin grams/L. The equivalent weight is generally calculated by dividingthe molecular weight in grams/mole by the number of functional groupsper molecules and is in grams/mole. For some molecules, such astriethylenetetramine (“TETA”) and 4,4′-diisocyanato-dicyclohexyl methane(“DES W”), the equivalent weight is equal to the molecular weightdivided by the number of functional groups per molecule. For example,TETA has a molecular weight of 146.23 g/mole and 4 amine groups.Therefore, the equivalent weight is 36.6 g/mol. This calculation isgenerally correct, but for some materials, the actual equivalent weightmay vary from the calculated equivalent weight. In some components, forexample, the biuret-containing adduct (i.e., trimer) ofhexamethylene-1,6-diisocyanate, the equivalent weight of thecommercially available material differs from the theoretical equivalentweight due to, for example, incomplete reaction. The theoreticalequivalent weight of the biuret-containing adduct (i.e., trimer) ofhexamethylene-1,6-diisocyanate is 159.5 g/mol. The actual equivalentweight of the trimer of hexamethylene-1,6-diisocyanate (“DES N3200”),the commercially available product, is about 183 g/mol. This actualequivalent weight is used in the calculations above. The actualequivalent weight may be obtained from the manufacturer or by titrationwith a suitable reactant by methods known in the art. The symbol, Σ, inthe amine molar equivalents calculation means that the amine molarequivalents comprises the sum of amine molar equivalents for allpolyamines in the reaction medium. Likewise, the symbol, Σ, in theisocyanate molar equivalents calculation means that the isocyanate molarequivalents comprises the sum of isocyanate molar equivalents for allpolyisocyanates in the reaction medium.

It is advantageous to select a polyamine component and a polyisocyanatecomponent such that the principal polyamine and optional auxiliarypolyamine has an amine functionality of at least 2, i.e., 3, 4, 5 ormore, and at least one of the polyisocyanates has an isocyanatefunctionality of at least 2, i.e., 2.5, 3, 4, 5, or more since highamine and isocyanate functionality increases the percentage ofcross-linking occurring between individual polyurea polymers thatcomprise the shell wall. In some embodiments, the principal polyamineand optional auxiliary polyamine has an amine functionality of greaterthan 2 and the polyisocyanate is a mixture of polyisocyanates whereineach polyisocyanate has an isocyanate functionality of greater than 2.In other embodiments the principal polyamine and optional auxiliarypolyamine comprises a trifunctional polyamine and the polyisocyanatecomponent comprises one or more trifunctional polyisocyanates. In yetother embodiments, the shell wall is formed by the reaction between apolyisocyanate or mixture of polyisocyanates with a minimum average of2.5 reactive groups per molecule and a principal polyamine and optionalauxiliary polyamine with an average of at least three reactive groupsper molecule. It is, moreover, advantageous to select concentrations ofthe polyamine component and the polyisocyanate component such that thepolyisocyanate component is substantially completely reacted to form thepolyurea polymer. Complete reaction of the polyisocyanate componentincreases the percentage of cross-linking between polyurea polymersformed in the reaction thereby providing structural stability to theshell wall. These factors, i.e., the ratio of weight of core materialcomponents compared to weight of shell wall components, the meanparticle sizes of the herbicidal microcapsules, the degree ofcrosslinking, among other factors, may be selected to affect the releaserate profile of the population of herbicidal microcapsules, therebyenabling the preparation of herbicidal microcapsules that balanceenhanced crop safety and are still efficacious for weed control.

Preferably, the molar equivalents ratio of amine molar equivalents toisocyanate molar equivalents is at least about 1.15:1 or even at leastabout 1.20:1. In some embodiments, the molar equivalents ratio is lessthan about 1.7:1, less than about 1.6:1, less than about 1.5:1, lessthan about 1.4:1, or even less than about 1.3:1. In some embodiments,the molar equivalents ratio of amine molar equivalents to isocyanatemolar equivalents in the polymerization medium is from 1.1:1 to about1.7:1, from 1.1:1 to about 1.6:1, from 1.1:1 to about 1.5:1, from 1.1:1to about 1.4:1, from 1.1:1 to about 1.3:1, from about 1.15:1 to about1.7:1, from about 1.15:1 to about 1.6:1, from about 1.15:1 to about1.5:1, from about 1.15:1 to about 1.4:1, or from about 1.15:1 to about1.3:1 Examples of typical ratios include 1.1, 1.15:1, 1.2:1, 1.25:1,1.3:1, 1.35:1, 1.4:1, 1.45:1 and 1.5:1. The molar equivalents ratio usedin the practice of the present invention is greater than that typicallyemployed in prior art compositions wherein a small stoichiometric excessof amine equivalents to isocyanate equivalents of about 1.01:1 to about1.05:1 is used to ensure that the isocyanate is completely reacted. Itis believed, without being bound to any particular theory, thatincreased excess of amine groups used in the present invention resultsin a significant number of unreacted amine functional groups therebyproviding a shell having a large number of amine functional groups thatare not cross-linked. It is believed, that the combination of acompletely reacted and cross-linked polyisocyanate component and anamine component having a significant number of unreacted anduncross-linked functional groups may result in a structurally stableshell wall that is more flexible and/or supple and less likely to shearor rupture as compared to shell walls known in the art. It is furtherbelieved that unreacted amine groups may reduce the number of fissuresor cracks in the shell wall thereby reducing leakage from the core.

In some other embodiments, the concentration of core material incomparison to the concentration of shell wall components in the reactionmedium is controlled thereby resulting in a variation of themicrocapsule shell wall thickness. Preferably, the reaction mediumcomprises core material and shell wall components in a concentration(weight) ratio from about 16:1 to about 3:1, such as from about 13:1 toabout 8:1, from about 13:1 to about 6:1, from about 12:1 to about 6:1,or from about 10:1 to about 6:1. The ratio is calculated by dividing thecore material concentration (grams/L), which consists of the herbicideactive and any diluent solvent or solvents, in the reaction medium bythe concentration of the shell wall components (grams/L) in the reactionmedium. The shell wall components concentrations comprises theconcentration of the polyamine component and the concentration of thepolyisocyanate component. In general, it has been found that decreasingthe ratio of core material to shell wall components tends to reduce, byincrease of shell wall thickness, the release rate of the corematerials. This tends to decrease both the crop injury and weed control,although the amounts of the effects are not always correlated.

In some embodiments, a diluent, such as a solvent, may be added tochange the solubility parameter characteristics of the core material toincrease or decrease the release rate of the active from themicrocapsule, once release has been initiated. For example, the corematerial may comprise from 0% to about 35% by weight of a diluent, forexample from 0.1 to about 25% by weight, from about 0.5% and about 20%by weight, or from about 1% and 10% by weight. In particular, the corematerial may comprise 0%, 0.5% 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 15%,20%, 25%, 30% or even 35% diluent. In some embodiments, the weight ratioof total core material to diluent can be, for example, from 8 to 1, from10 to 1, from 15 to 1, or from 20 to 1. In some embodiments, the diluentis a water-insoluble organic solvent having a solubility of less than10, 5, 1, 0.5 or even 0.1 gram per liter at 25° C. Examples of suitablewater-insoluble solvents include paraffinic hydrocarbons. Paraffinichydrocarbons are preferably predominantly a linear or branchedhydrocarbon. Examples include pentadecane and ISOPAR V.

A population of herbicidal microcapsules of the present invention may beprepared having at least one mean transverse dimension (e.g., diameteror mean particle size) of at least about 7 micrometers (“microns” orμm). The particle size may be measured with a laser light scatteringparticle size analyzer known to those skilled in the art. One example ofa particle size analyzer is a Coulter LS Particle Size Analyzer. Themicrocapsules are essentially spherical such that the mean transversedimension defined by any point on a surface of the microcapsule to apoint on the opposite side of the microcapsule is essentially thediameter of the microcapsule. Preferably, the population ofmicrocapsules has at least one mean transverse dimension, or meanparticle size, of at least about 7 μm, more preferably at least about 8μm, more preferably at least about 9 μm, more preferably at least about10 μm. In preferred embodiments, the mean particle size of thepopulation of microcapsules is less than about 15 μm, and morepreferably less than 12 μm. In view thereof, a population of herbicidalmicrocapsules of the present invention preferably has a mean particlesize of from about 7 μm to about 15 μm, from about 7 μm to about 12 μm,from about 8 μm to about 12 μm, or from about 9 μm to about 12 μm. Inparticularly preferred embodiments, the range varies from about 9 μm toabout 11 μm.

In some embodiments of the present invention, the compositions comprisea blend of a first population of a particulate microencapsulatedacetamide herbicide and a second population of a particulatemicroencapsulated acetamide herbicide. The first population ofmicroencapsulated acetamide herbicide has a mean particle size of fromabout 3 μm to about 11 μm, from about 4 μm to 11 μm, from about 5 μm to11 μm, from about 6 μm to 11 μm, from about 7 μm to 11 μm or from about8 μm to 11 μm. The second population of microencapsulated acetamideherbicide has a mean particle size of between 11 μm and about 20 μm,from 11.5 μm to about 20 μm, from 12 μm to about 20 μm, from 11.5 μm toabout 18 μm, from 12 μm to about 18 μm, from 11.5 μm to about 16 μm,from 12 μm to about 16 μm, from about 11.5 μm to about 15 μm, from 12 μmto about 15 μm, from 11.5 μm to about 14 μm or from 12 μm to about 14μm. The weight ratio of the first population of particulatemicroencapsulated acetamide herbicide to the second population ofparticulate microencapsulated acetamide herbicide is about 10:1, 5:1,3:1, 2:1, 1:1, 1:2, 1:3, 1:5 or about 1:10 and ranges thereof, such asfrom about 10:1 to about 1:10, from about 5:1 to about 1:5, from about3:1 to about 1:3 from about 2:1 to about 1:2 or is about 1:1. The ratioof amine molar equivalents contained in the polyamine component toisocyanate molar equivalents contained in the polyisocyanate component,as well as other characteristics and methods related to as describedherein for the microencapsulated acetamide herbicides, generally applyto both the first and second populations of particulatemicroencapsulated acetamides. In particular, the particle size shellwall characteristics for the first and second populations can beachieved as described above. It is believed, based on experimentalevidence to date, that release rate decreases with increasing shell wallamount (calculated on the basis of acetamide herbicide content) andparticle size. It is further believed that the release rate increaseswith increasing amine excess and ratio of acetamide to solvent (diluent,e.g., NORPAR). Release rate is generally decreased with an amine excessof from about 1% to about 10%, from about 2% to about 8% or from about3% to about 7% and an acetamide to solvent ratio of from 1 to 10, from 5to 10 or from 7 to 9. Release rate is generally increased with an amineexcess of from about 10% to about 30%, from about 15% to about 25% orfrom about 18% to about 22% and an acetamide to solvent ratio of from 10to 25, from 15 to 20 or from 17 to 19. The acetamide release rate for amixture of the first and second particulate microencapsulated acetamideherbicide blend can be measured according to the methods describedherein. A total acetamide release rate from the application mixturecomprising the blended first and second particulate microencapsulatedacetamide herbicide is preferably less than about 100 ppm afteragitation for 6 hours at 25° C. and less than about 150 ppm afteragitation for 24 hours at 25° C.; less than about 75 ppm after 6 hours,and less than about 125 ppm after 24 hours; less than about 60 ppm after6 hours, and less than about 100 ppm after 24 hours; or even less thanabout 50 ppm after 6 hours, and less than about 75 ppm after 24 hours.

An example of a blend of a first particulate microencapsulated acetamideherbicide and a second particulate microencapsulated acetamide herbicidethat provides a multi-modal (e.g., bimodal) release rate when combinedis as follows: (1) A first particulate microencapsulated acetamideherbicide wherein a population thereof has an acetochlor loading ofabout 33.0% by weight, a shell wall amount of about 8% (based onacetamide herbicide content), an amine excess over isocyanate of about20%, an acetochlor to paraffin oil ratio of about 18.5:1, and a meanparticle size of about 10 μm; and (2) A second particulatemicroencapsulated acetamide herbicide wherein a population thereof hasan acetochlor loading of about 41% by weight, a shell wall amount ofabout 7.1% (based on acetamide herbicide content), an amine excess overisocyanate of about 5%, an acetochlor to paraffin oil ratio of about8.4:1, and a mean particle size of from about 12 μm to about 13 μm. Ascompared to the particulate blend, the first population ofmicroencapsulated acetochlor herbicide particulates provides a fasterrelease rate and the second population of microencapsulated acetochlorherbicide particulates provides a slower release rate.

The particle size of the microcapsules of the present invention arelarger than that typically employed in the art and is generally achievedby varying the composition, as described above, and by controlling thereaction conditions such as, for example, blending speed, shear forces,mixer design and mixing times. In general, reduced blending speed, shearforces and mixing time favor the preparation of larger microcapsules.

In other embodiments of the present invention, two or more of the abovevariables can be manipulated in order to achieve the objects of thepresent invention. Manipulation of the following variable combinationsis within the scope of the present invention: (1) (i) the ratio of molarequivalent amine groups to isocyanate groups and (ii) the weight ratioof the core herbicide to the shell wall components; (2) (i) the ratio ofmolar equivalent amine groups to isocyanate groups and (iii) the weightratio of the core herbicide to the diluent (e.g., solvent); (3) (i) theratio of molar equivalent amine groups to isocyanate groups and (iv) themicrocapsule particle size; (4) (ii) the weight ratio of the coreherbicide to the shell wall components and (iii) the weight ratio of thecore herbicide to the diluent; (5) (ii) the weight ratio of the coreherbicide to the shell wall components and (iv) the microcapsuleparticle size; (6) (iii) the weight ratio of the core herbicide to thediluent and (iv) the microcapsule particle size; (7) (i) the ratio ofmolar equivalent amine groups to isocyanate groups, (ii) the weightratio of the core herbicide to the shell wall components, and (iii) theweight ratio of the core herbicide to the diluent; (8) (i) the ratio ofmolar equivalent amine groups to isocyanate groups, (ii) the weightratio of the core herbicide to the shell wall components, and (iv) themicrocapsule particle size; (9) (i) the ratio of molar equivalent aminegroups to isocyanate groups, (iii) the weight ratio of the coreherbicide to the diluent and (iv) the microcapsule particle size; (10)(ii) the weight ratio of the core herbicide to the shell wallcomponents, (iii) the weight ratio of the core herbicide to the diluentand (iv) the microcapsule particle size; and (11) (i) the ratio of molarequivalent amine groups to isocyanate groups, (ii) the weight ratio ofthe core herbicide to the shell wall components, (iii) the weight ratioof the core herbicide to the diluent and (iv) the microcapsule particlesize.

The release rate of the core material from the microcapsules can becontrolled by selecting capsule properties and composition and byselecting process parameters as previously described. Therefore, byappropriate choice of the parameters discussed previously and below, itis possible to create formulations that have acceptable safety whenapplied as a broadcast spray to a field either before crops are plantedor after planting, but before emergence and maintain good weed controlfor agriculturally useful lengths of time.

The microcapsules of the present invention exhibit a release rateprofile that provides a reduced rate of crop injury as compared tomicrocapsules known in the art. Under one theory, and without beingbound to any particular theory, it is believed that increasing the meanparticle size of the population of microcapsules decreases the totaleffective area per unit weight of the microcapsules. Since thediffusional release is proportional to the surface area, this tends, ifeverything else is held constant, to reduce the release rate. This inturn tends to reduce both the weed control and crop injury. However, ithas been surprisingly discovered that the microcapsules of the presentinvention provide crop plant injury that is even less than would beexpected based only on a particle size-mediated release rate. It isbelieved, without being bound to any particular theory, that thecombination of increased particle size and the shell characteristicsresulting from a large excess of unreacted amine groups significantlyreduces the amount of herbicide that the crop plants are exposed tofollowing a pre-planting or preemergent application, thereby providingenhanced crop safety and minimized crop plant injury. It is believedthat, as compared to prior art microcapsules, the flexible shell of thepresent invention is resistant to rupturing such that the amount ofherbicide that crop plants are initially exposed to upon application ofa herbicidal formulation containing the microcapsules is reduced.Additionally or alternatively, it is believed that the shell wall of themicrocapsules is characterized by reduced fissuring that decreasesleakage and flow of herbicide through the shell wall. In addition,optimizing the weight ratio of the core to the shell and the weightratio of the core herbicide to the diluent (solvent) may further affectrelease rate and achieve the objects of the present invention.

The release rate profile for the purposes of estimating the potentialfor crop injury of the herbicidal active from a population of herbicidalmicrocapsules of the present invention may be measured in the laboratoryusing an agitated dissolution test apparatus known in the art, such as aSOTAX AT-7 (SOTAX Corporation; Horsham, Pa. 19044) or a HANSON SR8-PLUS(available from Hitachi). In the dissolution rate method protocol of thepresent invention, an aqueous slurry consisting of 1% by weight of theencapsulated acetamide herbicide active ingredient in an aqueous mediumconsisting of deionized water is prepared. For example, a 100 mL aqueousslurry would contain a total of about 1 gram acetamide herbicide. Formicrocapsules comprising 50% by weight acetamide, the aqueous slurrytherefore would contain 2% by weight of the microcapsules. The aqueousslurry is placed a cell of the dissolution test apparatus and agitatedat a temperature of 25° C. The aqueous slurry is agitated at a ratesufficient to maintain the microcapsule particles in suspensionthroughout the test without mechanical rupture of the microcapsuleparticles. For example, in the case of a SOTAX AT-7 agitated dissolutiontest apparatus, the agitator is rotated at about 150 RPM. Aliquots areremoved periodically to determine the concentration of herbicide, e.g.,at 0, 1, 2, 4, 6, and 24 hours. Each aliquot is filtered through asyringe filter (TARGET Cellulose Acetate 0.2 μm, ThermoFisherScientific) to remove any capsules. The resulting solution is thenanalyzed for the active by standard analytical methods known in the art,such as, for instance, HPLC.

According to the method described herein for determining the releaserate profile and based on experimental evidence, it is believed thatgood crop safety correlates to an encapsulated acetamide herbicidecontained within a shell of limited permeability wherein a concentrationof acetamide herbicide (e.g., acetochlor) in the test aliquot at 6 hoursis less than about 100 ppm (about 1% of the total acetamide) and aconcentration of acetamide in the test aliquot at 24 hours is less thanabout 150 ppm (1.5% of the total acetamide. Preferably, theconcentration of acetamide in the test aliquot at 6 hours is less thanabout 75 ppm (0.75% of the total acetamide), and the concentration ofacetamide in the test aliquot at 24 hours is less than about 125 ppm(1.25% of the total acetamide). More preferably, the concentration ofacetamide in the test aliquot at 6 hours is less than about 60 ppm(0.60% of the total acetamide) and less than 100 ppm (1.00% of the totalacetamide) for the test aliquot at 24 hours. Even more preferably, theconcentration of acetamide in the test aliquot at 6 hours is less thanabout 50 ppm (0.50% of the total acetamide) and less than about 75 ppm(0.75% of the total acetamide) in the test aliquot at 24 hours. It hasbeen observed that herbicidal microcapsules having release rate profileswith the above-described parameters generally provide both commerciallyacceptable crop plant safety and efficacy on weeds. By comparison, asample of DEGREE Herbicide, a commercially available microencapsulatedacetochlor formulation available from Monsanto Company, typicallyreleases from about 125 ppm to about 140 ppm in the aliquot at 6 hoursand about 200 ppm (close to saturation) in the aliquot at 24 hours.

Preparation of the encapsulated acetamide herbicides of the presentinvention is described in more detail below.

Acetamide Encapsulation

The polyurea polymer shells of the present invention include a repeatunit having the general structure (I):

wherein X generally represents some portion, or portions, of the repeatunits which, as further defined herein below, may be independentlyselected from a number of different entities (e.g., differenthydrocarbylene linkers, such as aromatic, aliphatic, and cycloaliphaticlinking groups, and moieties having combinations of aromatic, aliphatic,and cycloaliphatic linking groups). The shell encapsulates anacetamide-containing core material such that, once initiated, moleculardiffusion of the acetamide through the shell wall is preferably thepredominant release mechanism (as further described elsewhere herein).Thus, the shell is preferably structurally intact; that is, the shell ispreferably not mechanically harmed or chemically eroded so as to allowthe acetamide to release by a flow mechanism. Further, the shell ispreferably substantially free of defects, such as micropores andfissures, of a size which would allow the core material to be releasedby flow. Micropores and fissures may form if gas is generated during amicrocapsule wall-forming reaction. For example, the hydrolysis of anisocyanate generates carbon dioxide. Accordingly, the microcapsules ofthe present invention are preferably formed in an interfacialpolymerization reaction in which conditions are controlled to minimizethe in situ hydrolysis of isocyanate reactants. The reaction variablesthat may preferably be controlled to minimize isocyanate hydrolysisinclude, but are not limited to: selection of isocyanate reactants,reaction temperature, and reaction in the presence of an excess of aminemolar equivalents over isocyanate molar equivalents.

As used herein, “flow” of the core material from the microcapsulegenerally refers to a stream of the material that drains or escapesthrough a structural opening in the shell wall. In contrast, “moleculardiffusion” generally refers to a molecule of, for example, anacetanilide, which is absorbed into the shell wall at the interiorsurface of the wall and desorbed from the shell wall at the exteriorsurface of the wall.

As described above, the polyurea polymer is preferably the product of areaction between a polyamine component comprising a principal polyamine(and optional auxiliary polyamine) having two or more amino groups permolecule and a polyisocyanate component comprising at least onepolyisocyanate having two or more isocyanate groups per molecule. Insome embodiments, the at least one polyisocyanate comprises a blend oftwo or more polyisocyanates. In some preferred embodiments, the blend ofpolyisocyanates comprises at least one diisocyanate, i.e., having twoisocyanate groups per molecule, and at least one triisocyanate, havingthree isocyanate groups per molecule. Preferably, neither the principalamine nor the auxiliary amine are the product of a hydrolysis reactioninvolving any of the polyisocyanates with which they react to form thepolyurea polymer. More preferably, the shell wall is substantially freeof a reaction product of a polyisocyanate with an amine generated by thehydrolysis of the polyisocyanate. This in situ polymerization of anisocyanate and its derivative amine is less preferred for a variety ofreasons described elsewhere herein.

The shell wall of the microcapsules may be considered “semi-permeable,”which, as used herein, generally refers to a microcapsule having ahalf-life that is intermediate between release from a substantiallyimpermeable microcapsule and a microcapsule that essentially allows theimmediate release of core material (i.e., a microcapsule having ahalf-life of less than about 24 hours, about 18 hours, about 12 hours,or even about 6 hours). For example, a “semi-permeable” microcapsule mayhave a half-life that is from about 5 to about 150 days, about 10 toabout 125 days, about 25 to about 100 days, or about 50 to about 75days.

Polyisocyanates

The polyurea polymer shell or wall of the microcapsules may be formedusing one or more polyisocyanates, i.e., having two or more isocyanategroups per molecule. In some embodiments, the polyurea shell wall isformed using a blend of at least two polyisocyanates. In a preferredembodiment, the polyurea shell wall is formed in an interfacialpolymerization reaction using at least one diisocyanate and at least onetriisocyanate.

Polyisocyanates for use in forming the shell wall of the presentinvention have the following general structure (II):R

N═C═O)_(n)  Structure (II)wherein n is an integer that is at least 2, such as from 2 to five, from2 to 4, and preferably is 2 or 3; and R is a group linking the 2 or moreisocyanate groups together, including any aromatic, aliphatic, orcycloaliphatic groups, or combinations of any of aromatic, aliphatic, orcycloaliphatic groups, which are capable of linking the isocyanategroups together.

A wide variety of aliphatic diisocyanates, cycloaliphatic diisocyanates,and aromatic diisocyanates (wherein X is two in structure (II)) may beemployed, for example, diisocyanates containing an aliphatic segmentand/or containing a cycloaliphatic ring segment or an aromatic ringsegment may be employed in the present invention as well.

General aliphatic diisocyanates include those having the followinggeneral structure (III):O═C═N—(CH₂)_(n)—N═C═O  Structure (III)wherein n is an integer having an mean value of from about 2 to about18, from about 4 to about 16, or about 6 to about 14. Preferably, n issix, i.e., 1,6-hexamethylene diisocyanate. The molecular weight of1,6-hexamethylene diisocyanate is about 168.2 g/mol. Since1,6-hexamethylene diisocyanate comprises 2 isocyanate groups permolecule, its equivalent weight is about 84.1 g/mol. The equivalentweight of the polyisocyanate is generally defined as the molecularweight divided by the number of functional groups per molecule. As notedabove, in some polyisocyanates, the actual equivalent weight may differfrom the theoretical equivalent weight, some of which are identifiedherein.

In certain embodiments, the aliphatic diisocyanates include dimers ofdiisocyanates, for example, a dimer having the following structure (IV):

wherein n is an integer having an mean value of from about 2 to about18, from about 4 to about 16, or about 6 to about 14. Preferably, n issix, i.e., structure (IV) is a dimer of 1,6-hexamethylene diisocyanate(molecular weight 339.39 g/mol; equivalent weight=183 g/mol).

A wide variety of cylcoaliphatic and aromatic diisocyanates may be usedas well. In general, aromatic diisocyanates include those diisocyanateswherein the R linking group contains an aromatic ring, and acycloaliphatic diisocyanates include those diisocyanates wherein the Rlinking group contains a cylcoaliphatic ring. Typically, the R groupstructure in both aromatic and cycloaliphatic diisocyanates containsmore moieties than just an aromatic or cycloaliphatic ring. Thenomenclature herein is used to classify diisocyanates.

Certain commercially available aromatic diisocyanates comprise twobenzene rings, which may be directly bonded to each other or connectedthrough an aliphatic linking group having from one to about four carbonatoms. One such aromatic diisocyanate is4,4′-diisocyanato-diphenylmethane (bis(4-isocyanatophenyl)methane(Molecular weight=250.25 g/mol; equivalent weight=125 g/mol) having thefollowing structure (V):

Aromatic diisocyanates having structures similar to structure (V)include 2,4′-diisocyanato-diphenylmethane (Molecular weight=250.25g/mol; equivalent weight=125 g/mol) and 2,2′-diisocyanato-diphenylmethane (Molecular weight=250.25 g/mol; equivalent weight=125 g/mol).

Other aromatic diisocyanates, wherein the benzene rings are directlybonded to each other include, 4,4′-diisocyanato-1,1′-biphenyl and4,4′-diisocyanato-3,3′-dimethyl-1,1′-biphenyl (Molecular weight=264.09g/mol; equivalent weight=132 g/mol), which has the following structure(VI):

Yet another aromatic diisocyanate is dianisidine diisocyanate(4,4′-diisocyanato-3,3′-dimethoxybiphenyl) (Molecular weight=296 g/mol;equivalent weight=148 g/mol) having the following structure (VII):

Certain commercially available aromatic diisocyanate comprise a singlebenzene ring. The isocyanate groups may be directly bonded to thebenzene ring or may be linked through aliphatic groups having from oneto about four carbon atoms. An aromatic diisocyanate having a singlebenzene ring is meta-phenylene diisocyanate (1,3-diisocyanatobenzene)(Molecular weight=160.1 g/mol; equivalent weight=80 g/mol) having thestructure (VIII):

Similar aromatic diisocyanates include para-phenylene diisocyanate(Molecular weight=160.1 g/mol; equivalent weight=80 g/mol), 2,4-toluenediisocyanate (2,4-diisocyanato-1-methylbenzene) (Molecular weight=174.2g/mol; equivalent weight=85 g/mol), 2,6-toluene diisocyanate (Molecularweight=174.2 g/mol; equivalent weight=85 g/mol), and2,4,6-triisopropyl-m-phenylene isocyanate. Similar diisocyanates havingaliphatic groups linking the isocyanates to the benzene ring include1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate,tetramethyl-meta-xylylene diisocyanate, tetramethyl-para-xylylenediisocyanate, and meta-tetramethylxylene diisocyanate(1,3-bis(2-isocyanatopropan-2-yl)benzene).

Cycloaliphatic diisocyanate may include one or more cycloaliphatic ringgroups having from four to about seven carbon atoms. Typically, thecycloaliphatic ring is a cyclohexane ring. The one or more cyclohexanerings may be bonded directly to each other or through an aliphaticlinking group having from one to four carbon atoms. Moreover, theisocyanate groups may be directly bonded to the cycloaliphatic ring ormay be linked through an aliphatic group having from one to about fourcarbon atoms. An example of a cycloaliphatic isocyanate is a4,4′-diisocyanato-dicyclohexyl methane(bis(4-isocyanatocyclohexyl)methane) such as Desmodur W (Miles) havingthe structure (IX):

Desmodur W has an approximate molecular weight of 262.35 and anapproximate equivalent weight of 131.2 g/mole. Additional cycloaliphaticdiisocyanates include 1,3-bis(isocyanatomethyl)cyclohexane andisophorone diisocyanate(5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane).

Certain aliphatic triisocyanates include, for example, trifunctionaladducts derived from linear aliphatic diisocyanates. The linearaliphatic diisocyanate may have the following structure (III):O═C═N—(CH₂)_(n)—N═C═O  Structure (III)wherein n is an integer having an mean value of from about 2 to about18, from about 4 to about 16, or about 6 to about 14. A particularlypreferred linear aliphatic diisocyanate of structure (III) useful forpreparing aliphatic triisocyanates is a trimer ofhexamethylene-1,6-diisocyanate. The aliphatic triisocyanates may bederived from the aliphatic isocyanate alone, i.e., dimers, trimers,etc., or they may be derived from a reaction between the aliphaticisocyanate of structure (I), and a coupling reagent such as water or alow molecular weight triol like trimethylolpropane, trimethylolethane,glycerol or hexanetriol.

An exemplary aliphatic triisocyanate, wherein n is 6, is thebiuret-containing adducts (i.e., trimers) ofhexamethylene-1,6-diisocyanate corresponding to the structure (X):

This material is available commercially under the trade name DesmodurN3200 (Miles) or Tolonate HDB (Rhone-Poulenc). Desmodur N3200 has anapproximate molecular weight of 478.6 g/mole. The commercially availableDesmodur N3200 has an approximate equivalent weight of 191 g/mol(Theoretical equivalent weight is 159 g/mol).

Another aliphatic triisocyanate derived from the aliphatic isocyanate ofstructure (III) corresponds to the following general structure:

A specific aliphatic triisocyanate of the above structure wherein the Rgroups are linear hydrocarbons having six carbon atoms (trimers ofhexamethylene-1,6-diisocyanate) having the name HDI isocyanurate trimer,which is available commercially under the trade names Desmodur N3300(Miles) or Tolonate HDT (Rhone-Poulenc). Desmodur N3300 has anapproximate molecular weight of 504.6 g/mol, and an equivalent weight of168.2 g/mol.

Another exemplary aliphatic triisocyanate is the triisocyanate adduct oftrimethylolpropane and hexamethylene-1,6-diisocyanate corresponding tothe structure (XII):

Aromatic triisocyanates containing an aromatic moiety are also useful inthe present invention, including for example those which contain orcomprise polymethylenepolyphenyl polyisocyanate (CAS #9016-87-9,4,4′-(4-isocyanato-1,3-phenylene) bis(methylene) s(isocyanatobenzene))having the structure (XIII):

Isocyanates with an aromatic moiety may have a tendency to undergo insitu hydrolysis at a greater rate than aliphatic isocyanates. Since therate of hydrolysis is decreased at lower temperatures, isocyanatereactants are preferably stored at temperatures no greater than about50° C., and isocyanate reactants containing an aromatic moiety arepreferably stored at temperatures no greater than about 20° C. to about25° C., and under a dry atmosphere.

Still other polyisocyanates include toluene diisocyanate adducts withtrimethylolpropane, xylene diisocyanate and polymethylenepolyphenylpolyisocyanate-terminated polyols.

It is to be noted that selection of the polyisocyanate, or blend ofpolyisocyanates, to be used may be determined experimentally using meansknown in the art (see, e.g., U.S. Pat. No. 5,925,595, the entirecontents of which are incorporated herein for all relevant purposes).Where a blend of a triisocyanate and a diisocyanate is used, the ratioof the triisocyanate to the diisocyanate, on an isocyanate equivalentbasis, is between about 90:10 and about 30:70.

Amines

A. Principal Amines

In some preferred embodiments of the present invention, the polyaminecomponent consists essentially of the principal amine. Similarly stated,in some embodiments, the polyamine component is a principal amine in theabsence of one or more auxiliary amines. The polyurea polymers, fromwhich the microcapsule shell wall is prepared or formed, may comprise anamine or polyfunctional amine precursor (e.g., monomer). Among theamines or polyfunctional amines that may be employed to prepare apreferred microcapsule of the present invention are, for example, linearalkylamines or polyalkylamines, having the general structure:H₂N—X—NH₂  Structure (XIV)wherein “X” is selected from the group consisting of —(CH₂)_(a)— and—(C₂H₄)—Y—(C₂H₄); “a” is an integer having a value from about 1 to about8, 2 to about 6, or about 3 to about 5; and, “Y” is selected from thegroup consisting of —S—S—, —(CH₂)_(b)—Z—(CH₂)_(b)—, and —Z—(CH₂)_(a)—Z—,wherein “b” is an integer having a value from 0 to 4, or from 1 to 3,“a” is as defined above, and “Z” is selected from the group consistingof

Examples of such amines or polyfunctional amines that may typically beemployed in the present invention include substituted and unsubstitutedpolyethyleneamines, such as (i) amines of the structure NH₂(CH₂CH₂NH)_(m)CH₂CH₂NH₂ where m is 1 to 5, 1 to 3, or 2, (ii) diethylenetriamine (molecular weight=103.17 g/mol, equivalent weight=34.4 g/mol)and (iii) triethylene tetramine (molecular weight=146.23 g/mol,equivalent weight=36.6 g/mol), as well as substituted and unsubstitutedpolypropylenimines. However, it is to be noted that other, similarsubstituted and unsubstituted polyfunctional amines are also useful,including for example iminobispropylamine, bis(hexamethylene)triamine,cystamine, triethylene glycol diamine (e.g. Jeffamine EDR-148 fromHuntsman Corp., Houston, Tex.) and the alkyl diamines, triamine andtetramine having a main alkyl chain of from about 2 to about 6, or about2 to about 4, carbons in length (e.g., from ethylene diamine up tohexamethylene diamine, triamine or tetramine, with a few number ofcarbons typically being preferred and/or tetramines typically beingpreferred over triamines). The principal polyamine may comprise one ormore of any of the above described amines having the general structure(XIV). Among the preferred amines are included, for example, substitutedor unsubstituted polyethyleneamine, polypropyleneamine, diethylenetriamine and triethylene tetramine.

B. Auxiliary Amines

In some optional embodiments of the present invention, the polyaminecomponent comprises a principal amine and one or more auxiliary amines.Where the polyamine component comprises a principal amine and anauxiliary amine, the permeability of the shell wall, or the release rateof the core material, may be affected, for example, by varying therelative amounts of 2 or more amines used in the shell wall-formingpolymerization reaction (see, e.g., U.S. Patent Pub. No. 2004/0137031A1, the entire contents of which is incorporated by reference herein).Accordingly, in addition to those principal amines set forth above,auxiliary amines, such as a polyalkyleneamine or an epoxy-amine adduct,may be optionally included in combination with the principal amine toprovide microcapsules having an altered shell wall permeability orrelease rate as compared to a shell wall prepared from an amine sourceconsisting essentially of a principal amine, in addition to thepermeability imparted thereto upon activation of the microcapsule (e.g.,by cleavage of the blocking group from the polymer backbone).

This permeability, or release rate, may change (e.g., increase) as theratio of the auxiliary amine to a principal amine increases. It is to benoted, however, that alternatively or additionally, as described ingreater detail elsewhere herein, the rate of permeability may be furtheroptimized by altering the shell wall composition by, for example, (i)the type of isocyanate employed, (ii) using a blend of isocyanates,(iii) using an amine having the appropriate hydrocarbon chain lengthbetween the amino groups, and/or (iv) varying the ratios of the shellwall components and core components, all as determined, for example,experimentally using means standard in the art.

In some embodiments, the permeability-altering or auxiliary amine may bea polyalkyleneamine prepared by reacting an alkylene oxide with a diolor triol to produce a hydroxyl-terminated polyalkylene oxideintermediate, followed by amination of the terminal hydroxyl groups.

Alternatively, the auxiliary amine may be a polyetheramine(alternatively termed a polyoxyalkyleneamine, such as for examplepolyoxypropylenetri- or diamine, and polyoxyethylenetri- or diamine)having the following structure (XV):

wherein: c is a number having a value of 0 or 1; “R¹” is selected fromthe group consisting of hydrogen and CH₃(CH₂)_(d)—; “d” is a numberhaving a value from 0 to about 5; “R²” and “R³” are

respectively; “R⁴” is selected from the group consisting of hydrogen and

wherein “R⁵”, “R⁶”, and “R⁷” are independently selected from a groupconsisting of hydrogen, methyl, and ethyl; and, “x”, “y”, and “z” arenumbers whose total ranges from about to 2 to about 40, or about 5 toabout 30, or about 10 to about 20.

In some embodiments, the value of x+y+z is preferably no more than about20, or more preferably no more than about 15 or even about 10. Examplesof useful auxiliary amine compounds having this formula include aminesof the Jeffamine ED series (Huntsman Corp., Houston, Tex.). One of suchpreferred amines is Jeffamine T-403 (Huntsman Corp., Houston, Tex.),which is a compound according to this formula wherein c, g and h areeach 0, R1 is CH₃CH₂ (i.e., CH₃(CH₂)d, where d is 1), R₅, R₆, and R₇ areeach a methyl group and the average value of x+y+z is from about 5 andabout 6.

The reaction of a polyfunctional amine with an epoxy functional compoundhas been found to produce epoxy-amine adducts that are also useful asauxiliary amines. Epoxy-amine adducts are generally known in the art.(See, e.g., Lee, Henry and Neville, Kris, Aliphatic Primary Amines andTheir Modifications as Epoxy-Resin Curing Agents in Handbook of EpoxyResins, pp. 7-1 to 7-30, McGraw-Hill Book Company (1967).) Preferably,the adduct has a water solubility as described for amines elsewhereherein. Preferably, the polyfunctional amine which is reacted with anepoxy to form the adduct is an amine as previously set forth above. Morepreferably, the polyfunctional amine is diethylenetriamine orethylenediamine. Preferred epoxies include ethylene oxide, propyleneoxide, styrene oxide, and cyclohexane oxide. Diglycidyl ether ofbisphenol A (CAS #1675-54-3) is a useful adduct precursor when reactedwith an amine in an amine to epoxy group ratio preferably of at leastabout 3 to 1.

It is to be noted, however, that permeability may also be decreased insome instances by the addition of an auxiliary amine. For example, it isknown that the selection of certain ring-containing amines as thepermeability-altering or auxiliary amine is useful in providingmicrocapsules with release rates which decrease as the amount of such anamine increases, relative to the other, principal amine(s) therein.Preferably, the auxiliary amine is a compound selected from the groupconsisting of cycloaliphatic amines and arylalkyl amines. Aromaticamines, or those having the nitrogen of an amine group bonded to acarbon of the aromatic ring, may not be universally suitable. Exemplary,and in some embodiments preferred, cycloaliphatic amines include4,4′-diaminodicyclohexyl methane, 1,4-cyclohexanebis(methylamine) andisophorone diamine (5-Amino-1,3,3-trimethylcyclohexanemethylamine;molecular weight=170.30 g/mol; equivalent weight=85.2 g/mol). Exemplary,and in some embodiments preferred, arylalkyl amines have the structureof the following structure (XVI):

wherein “e” and “f” are integers with values which independently rangefrom about 1 to about 4, or about 2 to about 3. Meta-xylylene diamine,from Mitsubishi Gas Co., Tokyo, JP, is a preferred example of anarylalkyl amine (molecular weight=136.19 g/mol; equivalent weight=68.1g/mol). Another example is para-xylylenediamine. Alkyl substitutedarylalkyl polyamines include 2,3,5,6-tetramethyl-1,4-xylylenediamine and2,5-dimethyl-1,4-xylylenediamine.C. Amine Properties

Preferably, the principal amine (and optional auxiliary polyamine) hasat least about two amino groups or functionalities, and even morepreferably, the amine comprises at least three amino groups. Withoutbeing held to any particular theory, it is generally believed that in aninterfacial polymerization as described herein, the effectivefunctionality of a polyfunctional amine is typically limited to onlyslightly higher than about 2 and less than about 4. This is believed tobe due to steric factors, which normally prevent significantly more thanabout 3 amino groups in the polyfunctional amine shell wall precursorfrom participating in the polymerization reaction.

It is to be further noted that the molecular weight of the aminemonomer, which may or may not possess an amine blocking group thereon,is preferably less than about 1000 g/mole, and in some embodiments ismore preferably less than about 750 g/mole or even 500 g/mole. Forexample, the molecular weight of the amine monomer, which may or may nothave one or more block amine functionalities therein, may range fromabout 75 g/mole to less than about 750 g/mole, or from about 100 g/moleto less than about 600 g/mole, or from about 150 g/mole to less thanabout 500 g/mole. Equivalent weights (the molecular weight divided bythe number of amine functional groups) generally range from about 20g/mole to about 250 g/mole, such as from about 30 g/mole to about 125g/mole. Without being held to a particular theory, it is generallybelieved that steric hindrance is a limiting factor here, given thatbigger molecules may not be able to diffuse through the early-formingproto-shell wall to reach, and react to completion with, the isocyanatemonomer in the core during interfacial polymerization.

Core Material Composition

Generally speaking, useful herbicidal core materials include those thatare a single phase liquid at temperatures of less than about 80° C.Preferably, the core material is a liquid at temperatures of less thanabout 65° C. More preferably, the core material is a liquid attemperatures of less than about 50° C. The core material may alsocomprise solids suspended in a liquid phase. Whether liquid or solids ina liquid phase, the core material preferably has a viscosity such thatit flows easily to facilitate transport by pumping and to facilitate thecreation of an oil in water emulsion as part of the method forpreparation of microcapsules discussed herein. Thus, the core materialpreferably has a viscosity of less than about 1000 centipoise (cps)(e.g., less than about 900, 800, 700, 600 or even 500 cps) at thetemperature at which the emulsion is formed and the polymerizationreaction occurs, typically from about 25° C. to about 65° C., typically,from about 40° C. to about 60° C. Preferably, the core material iswater-immiscible, a property which promotes encapsulation by interfacialpolymerization. Water-immiscibility refers to materials that have arelatively low water solubility at about 25° C., for example, less thanabout 500 mg/L, preferably less than about 250 mg/L, even morepreferably less than about 100 mg/L. Certain core materials have evenlower water solubilities, such as acetochlor, which is less than 25 mg/Lat 25° C. In some preferred embodiments, the acetamide herbicidal corematerials suitable for the practice of the present invention includedimethenamid, napropamide, pronamide and acetanilide herbicides such asacetochlor, alachlor, butachlor, butenachlor, delachlor, diethatyl,dimethachlor, mefenacet, metazochlor, metolachlor, pretilachlor,propachlor, propisochlor, prynachlor, terbuchlor, thenylchlor andxylachlor, mixtures thereof and stereoisomers thereof. Preferredacetamide herbicides include dimethenamid and dimethenamid-P andpreferred acetanilide herbicides include acetochlor, metolachlor andS-metolachlor.

The core material may comprise multiple compounds for release (e.g., anacetamide and one or more additives compatible therewith which act toenhance its bioefficacy on weeds and/or reduce crop injury). Forexample, in some embodiments, the core material optionally comprises asafener. Suitable safeners include, for example, furilazole((RS)-3-(dichloroacetyl)-5-(2-furanyl)-2,2-dimethyl-1,3-oxazolidine95%), commercially available from Monsanto Company; AD 67(4-(dichloroacetyl)-1-oxa-4-azaspiro[4, 5]decane); benoxacor (CGA154281, (RS)-4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine);cloquintocet-mexyl (CGA 184927, (5-chloroquinolin-8-yloxy)acetic acid);cyometrinil (CGA 43089, (Z)-cyanomethoxyimino(phenyl)acetonitrile);cyprosulfamide (N-[4-(cyclopropylcarbamoyl)phenylsulfonyl]-o-anisamide);dichlormid (DDCA, R25788, N, N-diallyl-2, 2-dichloroacetamide);dicyclonon((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one);dietholate (O,O-diethyl O-phenyl phosphorothioate) fenchlorazole-ethyl(HOE 70542,1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylicacid); fenclorim (CGA 123407 4, 6-dichloro-2-phenylpyrimidine);flurazole (benzyl2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate); fluxofenim (CGA133205, 4′-chloro-2,2,2-trifluoroacetophenone(EZ)-O-1,3-dioxolan-2-ylmethyloxime); isoxadifen(4,5-dihydro-5,5-diphenyl-1,2-oxazole-3-carboxylic acid); mefenpyr((RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylicacid); mephenate (4-chlorophenyl methylcarbamate); MG 191; naphthalicanhydride; oxabetrinil (CGA 92194,(Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile); and others asare known in the art. It is to be noted that the herbicidalmicrocapsules, through selection of processing and structuralparameters, achieve commercially acceptable crop safety even in theabsence of a safener. Therefore, the safener is an optional corematerial.

It is to be further noted, as previously described, that the corematerial may optionally comprise a diluent. The diluent may be added tochange the solubility parameter characteristics of the core material toincrease or decrease the release rate of the active from themicrocapsule, once release has been initiated. The preferred diluentcontent in the core material is as previously described.

The diluent may be selected from essentially any of those known in theart. The compatibility of the diluent with the core material (e.g., theacetamide active) and/or the shell wall may be determined, for example,experimentally using means standard in the art (see, e.g., U.S. PatentPub. No. 2004/0137031 A1 and U.S. Pat. No. 5,925,595, the entirecontents of which are incorporated herein for all relevant purposes).Exemplary diluents include, for example: alkyl-substituted biphenylcompounds (e.g., SureSol 370, commercially available from Koch Co.);normal paraffin oil (e.g., NORPAR 15, commercially available fromExxon); mineral oil (e.g., ORCHEX 629, commercially available fromExxon); isoparaffin oils (e.g., ISOPAR V and ISOPAR L, commerciallyavailable from Exxon); aliphatic fluids or oils (e.g., EXXSOL D110 andEXXSOL D130, commercially available from Exxon); alkyl acetates (e.g.,EXXATE 1000, formerly commercially available from Exxon); aromaticfluids or oils (A 200, commercially available from Exxon); citrateesters (e.g., Citroflex A4, commercially available from Morflex); and,plasticizing fluids or oils used in, for examples, plastics (typicallyhigh boiling point esters).

Preparation of Microcapsules and Dispersions Thereof

In general, an aqueous dispersion of the microcapsules of the presentinvention may be produced by an interfacial polymerization reaction,either continuously or batchwise, using means generally known in theart. However, preferably a principal amine is polymerized with one ormore polyisocyanates at the interface of an oil-in-water emulsion. Thediscontinuous oil phase (also referred to herein as “internal phase”)preferably comprises one or more polyisocyanates and a continuousaqueous phase (also referred to herein as “external phase”) comprisesthe principal amine. The oil phase further comprises a core materialthat preferably comprises an acetamide herbicide as the activeingredient. In other embodiments, when more than one amine is used(e.g., a principal amine and an auxiliary amine), these amines may bereacted in a ratio such that the microcapsules have a predeterminedpermeability with respect to the core material, either prior toactivation or additionally upon activation.

In this regard it is to be noted that preferably the amine is not thehydrolysis product of the isocyanate. Rather, it is preferred that thereactants are selected from, for example, the amines and polyisocyanatesdisclosed elsewhere herein.

The oil-in-water emulsion is preferably formed by adding the oil phaseto the continuous aqueous phase to which an emulsifying agent has beenadded (e.g., previously dissolved therein). The emulsifying agent isselected to achieve the desired oil droplet size in the emulsion. Thesize of the oil droplets in the emulsion is impacted by a number offactors in addition to the emulsifying agent employed and determines thesize of microcapsules formed by the process, as described elsewhereherein. The emulsifying agent is preferably a protective colloid.Polymeric dispersants are preferred as protective colloids. Polymericdispersants provide steric stabilization to an emulsion by adsorbing tothe surface of an oil drop and forming a high viscosity layer whichprevents drops from coalescing. Polymeric dispersants may be surfactantsand are preferred to surfactants which are not polymeric, becausepolymeric compounds form a stronger interfacial film around the oildrops. If the protective colloid is ionic, the layer formed around eachoil drop will also serve to electrostatically prevent drops fromcoalescing. SOKALAN (BASF), a maleic acid-olefin copolymer, is apreferred protective colloid, as is Invalon and Lomar D (Cognis).

Other protective colloids useful in this invention are gelatin, casein,polyvinyl alcohol, alkylated polyvinyl pyrrolidone polymers, maleicanhydride-methyl vinyl ether copolymers, styrene-maleic anhydridecopolymers, maleic acid-butadiene and diisobutylene copolymers, sodiumand calcium lignosulfonates, sulfonated naphthalene-formaldehydecondensates, modified starches, and modified cellulosics likehydroxyethyl or hydroxypropyl cellulose, and carboxy methyl cellulose.

To prepare microcapsules of a preferred mean diameter, the selection ofa protective colloid and the conditions of the emulsification step areto be given consideration. For example, the quality of the emulsion, andhence the size of the microcapsules produced, is dependent to someextent upon the stirring operation used to impart mechanical energy tothe emulsion. Preferably, the emulsification is accomplished with a highshear disperser. Generally, the microcapsules produced by this processhave a size roughly approximated by the size of the oil drops from whichthey formed. Therefore, the emulsion is typically mixed to create oildrops having a mean diameter preferably at least about 5 μm, buttypically less than about 15 μm.

The time that the emulsion remains in a high shear mixing zone ispreferably limited to only the time required to create an emulsionhaving the desired droplet size. The longer the emulsion remains in thehigh shear mixing zone, the greater the degree to which thepolyisocyanate will hydrolyze and react in situ. A consequence of insitu reaction is the premature formation of shell walls. Shell wallsformed in the high shear zone may be destroyed by the agitationequipment, resulting in wasted raw materials and an unacceptably highconcentration of unencapsulated core material in the aqueous phase.Typically, mixing the phases with a Waring blender for about 45 secondsto about 90 seconds, or with an in-line rotor/stator disperser having ashear zone dwell time of much less than a second, is sufficient. Aftermixing, the emulsion is preferably agitated sufficiently to maintain avortex.

The time at which the amine source is added to the aqueous phase is aprocess variable that may affect, for example, the size distribution ofthe resulting microcapsules and the degree to which in situ hydrolysisoccurs. Contacting the oil phase with an aqueous phase which containsthe amine source prior to emulsification initiates some polymerizationat the oil/water interface. If the mixture has not been emulsified tocreate droplets having the preferred size distribution, a number ofdisfavored effects may result, including but not limited to: thepolymerization reaction wastefully creates polymer which is notincorporated into shell walls; oversized microcapsules are formed; or,the subsequent emulsification process shears apart microcapsules whichhave formed.

In some instances, the negative effects of premature amine addition maybe avoided by adding a non-reactive form of the amine to the aqueousphase and converting the amine to its reactive form after emulsion. Forexample, the salt form of amine reactants may be added prior toemulsification and thereafter converted to a reactive form by raisingthe pH of the emulsion once it is prepared. This type of process isdisclosed in U.S. Pat. No. 4,356,108, which is herein incorporated byreference in its entirety. However, it is to be noted that the increasein pH required to activate amine salts may not exceed the tolerance ofthe protective colloid to pH swings, otherwise the stability of theemulsion may be compromised.

Accordingly, it may be preferable for the amine source to be added afterthe preparation of the emulsion. More preferably, the amine source maybe added as soon as is practical after a suitable emulsion has beenprepared. Otherwise, the disfavored in situ hydrolysis reaction may befacilitated for as long as the emulsion is devoid of amine reactant,because the reaction of isocyanate with water proceeds unchecked by anypolymerization reaction with amines. Therefore, amine addition ispreferably initiated and completed as soon as practical after thepreparation of the emulsion.

There may be, however, situations where it is desirable to purposefullyincrease the period over which the amine source is added. For example,the stability of the emulsion may be sensitive to the rate at which theamine is added. Alkaline colloids, like SOKALAN, can generally handlethe rapid addition of amines. However, rapid addition of amines to anemulsion formed with non-ionic colloids or PVA cause the reactionmixture to gel rather than create a dispersion. Furthermore, ifrelatively “fast reacting” polyisocyanates are used (e.g.,polyisocyanates containing an aromatic moiety), gelling may also occurif the amines are added too quickly. Under the above circumstances, itis typically sufficient to extend the addition of the amine over aperiod of from about 3 to about 15 minutes, or from about 5 to about 10minutes. The addition is still preferably initiated as soon as ispractical after the emulsion has been prepared.

The viscosity of the external phase is primarily a function of theprotective colloid present. The viscosity of the external phase ispreferably less than about 50 cps, more preferably less than about 25cps, and still more preferably less than about 10 cps at the temperatureof emulsion preparation, which is typically from about 25° C. to about65° C., preferably from about 40° C. to about 60° C. The external phaseviscosity is measured with a Brookfield viscometer with a spindle size 1or 2 and at about 20 to about 60 rpm speed. After reaction and withoutadditional formulation, the microcapsule dispersion which is prepared bythis process preferably has a viscosity of less than about 400 cps(e.g., less than about 350 cps, about 300 cps, about 250 cps, or evenabout 200 cps) at the temperature of emulsion preparation. Morepreferably the dispersion viscosity is from about 100 to about 200 cps,or from 125 to about 175 cps at the temperature of emulsion preparation.

It is preferred that the oil phase is in the liquid state as it isblended into the aqueous phase. Preferably, the acetamide herbicide orother active ingredient is melted or dissolved or otherwise prepared asliquid solution prior to the addition of the isocyanate reactant. Tothese ends, the oil phase may require heating during its preparation.

The discontinuous oil phase may also be a liquid phase which containssolids. Whether liquid, low melting solid, or solids in a liquid, thediscontinuous oil phase preferably has a viscosity such that it flowseasily to facilitate transport by pumping and to facilitate the creationof the oil-in-water emulsion. Thus, the discontinuous oil phasepreferably has a viscosity of less than about 1000 cps (e.g., less thanabout 900 cps, about 800 cps, about 700 cps, about 600 cps, or evenabout 500 cps) at the temperature of emulsion preparation, which istypically from about 25° C. to about 65° C., preferably from about 40°C. to about 60° C.

To minimize isocyanate hydrolysis and in situ shell wall formation, acooling step subsequent to heating the oil phase is preferred when theoil phase comprises a polyisocyanate comprising an aromatic moiety,because isocyanates comprising an aromatic moiety undergo thetemperature-dependent hydrolysis reaction at a faster rate thannon-aromatic isocyanates. It has been discovered that the hydrolysisreaction has a negative effect on the preparation of the microcapsulesof the present invention. Among other problems, isocyanates hydrolyze toform amines that compete in situ with the selected amine in thepolymerization reaction, and the carbon dioxide generated by thehydrolysis reaction may introduce porosity into the preparedmicrocapsules. Therefore, it is preferred to minimize the hydrolysis ofisocyanate reactants at each step of the process of the presentinvention. Since the hydrolysis reaction rate is directly dependent onthe temperature, it is particularly preferred that the internal phase(i.e., discontinuous phase) be cooled to less than about 50° C.subsequent to mixing the polyisocyanate and the core material. It isalso preferred that the internal phase be cooled to less than about 25°C. if isocyanates comprising an aromatic moiety are used.

Hydrolysis may also be minimized by avoiding the use of oil phasecompositions in which water is highly soluble. Preferably water is lessthan about 5% by weight soluble in the oil phase at the temperature ofthe emulsion during the reaction step. More preferably water is lessthan about 1% soluble in the oil phase. Still more preferably water isless than about 0.1% soluble in the oil phase. It is preferred that theoil phase has a low miscibility in water. Low miscibility in water alsopromotes the formation of a useful emulsion.

It is preferred that the principal polyamine (and optional auxiliarypolyamine) is sufficiently mobile across an oil-water emulsioninterface. Thus, it is preferred that amines selected for thewall-forming reaction have an n-octanol/water partition coefficientwherein the base-10 log of the partition coefficient is between about −4and about 1. It is also preferred that the reaction occur on the oilside of the oil-water interface, but is it believed that at partitioncoefficient values lower than about −4 the amines may not be solubleenough in the oil phase to participate sufficiently in the wall-formingreaction. Therefore, the reaction may proceed too slowly to beeconomical, or the disfavored in situ reaction may predominate.Furthermore, at partition coefficient values above about 1, the aminesmay not be sufficiently soluble in the water phase to be evenlydistributed enough throughout the aqueous phase to facilitate aconsistent reaction rate with all the oil particles. Therefore, morepreferably the base-10 log of the partition coefficient is between about−3 and about 0.25, or about −2 and about 0.1.

To further reduce the amount of poyisocyanate hydrolysis and in situreaction, the reaction is preferably run at as low of a temperature aseconomics based on the reaction rate will allow. For example, thereaction step may preferably be performed at a temperature from about40° C. to about 65° C. More preferably, the reaction step may beperformed at a temperature from about 40° C. to about 50° C.

The reaction step may preferably be performed to convert at least about90% of the polyisocyanate. The reaction step may more preferably beperformed to convert at least about 95% of the polyisocyanate. In thisregard it is to be noted that the conversion of polyisocyanate may betracked by monitoring the reaction mixture around an isocyanate infraredabsorption peak at 2270 cm⁻¹, until this peak is essentially no longerdetectable. The reaction may achieve 90% conversion of the isocyanate ata reaction time which is within the range of, for example, aboutone-half hour to about 3 hours, or about 1 to about 2 hours, especiallywhere the core material comprises an acetanilide.

Liquid Microcapsule Dispersions: Parameters and Compositions

The microcapsules of the present invention comprise a water-immiscible,agricultural chemical-containing core material encapsulated by apolyurea shell wall, which is preferably substantially non-microporous,such that core material release occurs by a molecular diffusionmechanism, as opposed to a flow mechanism through a pore or rift in thepolyurea shell wall. As noted herein, the shell wall may preferablycomprise a polyurea product of a polymerization of one or morepolyisocyanates and a principal polyamine (and optional auxiliarypolyamine). Additionally, a further embodiment of the present inventioncomprises a liquid dispersion of the microcapsules of the presentinvention. The liquid medium in which the microcapsules are dispersed ispreferably aqueous (e.g., water). The dispersion may optionally, and/orpreferably, be further formulated with additives as described elsewhereherein (e.g., a stabilizer, one or more surfactants, an antifreeze, ananti-packing agent, drift control agents, etc.).

The acetamide herbicide loading of the formulated microcapsuledispersions of the present invention is typically from about 5% to about50% by weight on an active ingredient basis, such as 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45% or even 50% by weight on an active ingredientbasis. In application mixture formulations, the acetamide herbicideloading is typically no more than about 5% by weight or from about 0.1%to about 5% by weight on an active ingredient basis, such as 5%, 4%, 3%,2%, 1%, 0.5% or 0.1% by weight on an active ingredient basis.

The aqueous dispersion of microcapsules of the present invention maypreferably be formulated to further optimize its shelf stability andsafe use. Dispersants and thickeners are useful to inhibit theagglomeration and settling of the microcapsules. This function isfacilitated by the chemical structure of these additives as well as byequalizing the densities of the aqueous and microcapsule phases.Anti-packing agents are useful when the microcapsules are to beredispersed. A pH buffer can be used to maintain the pH of thedispersion in a range which is safe for skin contact and, depending uponthe additives selected, in a narrower pH range than may be required forthe stability of the dispersion.

Low molecular weight dispersants may solubilize microcapsule shellwalls, particularly in the early stages of their formation, causinggelling problems. Thus, in some embodiments dispersants havingrelatively high molecular weights of at least about 1.5 kg/mole, morepreferably of at least about 3 kg/mole, and still more preferably atleast about 5, 10 or even 15 kg/mole. In some embodiments, the molecularweight may range from about 5 kg/mole to about 50 kg/mole. Dispersantsmay also be non-ionic or anionic. An example of a high molecular weight,anionic polymeric dispersant is polymeric naphthalene sulfonate sodiumsalt, such as Invalon (formerly Irgasol, Huntsman Chemicals). Otheruseful dispersants are gelatin, casein, ammonium caseinate, polyvinylalcohol, alkylated polyvinyl pyrrolidone polymers, maleicanhydride-methyl vinyl ether copolymers, styrene-maleic anhydridecopolymers, maleic acid-butadiene and diisobutylene copolymers, sodiumand calcium lignosulfonates, sulfonated naphthalene-formaldehydecondensates, modified starches, and modified cellulosics likehydroxyethyl or hydroxypropyl cellulose, and sodium carboxy methylcellulose.

Thickeners are useful in retarding the settling process by increasingthe viscosity of the aqueous phase. Shear-thinning thickeners may bepreferred, because they act to reduce dispersion viscosity duringpumping, which facilitates the economical application and even coverageof the dispersion to an agricultural field using the equipment commonlyemployed for such purpose. The viscosity of the microcapsule dispersionupon formulation may preferably range from about 100 cps to about 400cps, as tested with a Haake Rotovisco Viscometer and measured at about10° C. by a spindle rotating at about 45 rpm. More preferably, theviscosity may range from about 100 cps to about 300 cps. A few examplesof useful shear-thinning thickeners include water-soluble, guar- orxanthan-based gums (e.g. Kelzan from CPKelco), cellulose ethers (e.g.ETHOCEL from Dow), modified cellulosics and polymers (e.g. Aqualonthickeners from Hercules), and microcrystalline cellulose anti-packingagents.

Adjusting the density of the aqueous phase to approach the mean weightper volume of the microcapsules also slows down the settling process. Inaddition to their primary purpose, many additives may increase thedensity of the aqueous phase. Further increase may be achieved by theaddition of sodium chloride, glycol, urea, or other salts. The weight tovolume ratio of microcapsules of preferred dimensions is approximated bythe density of the core material, where the density of the core materialis from about 1.05 to about 1.5 g/cm³. Preferably, the density of theaqueous phase is formulated to within about 0.2 g/cm³ of the mean weightto volume ratio of the microcapsules. More preferably, the density ofthe aqueous phase ranges from about 0.2 g/cm³ less than the weight meanweight to volume ratio of the microcapsules to about equal to the weightmean weight to volume ratio of the microcapsules.

In order to enhance shelf stability and prevent gelling of the aqueousdispersion of microcapsules, particularly upon storage in hightemperature environments, the formulated microcapsule dispersions mayfurther include urea or similar structure-breaking agent at aconcentration of up to about 20% by weight, typically about 5% byweight.

Surfactants can optionally be included in the formulated microcapsuledispersions of the present invention. Suitable surfactants are selectedfrom non-ionics, cationics, anionics and mixtures thereof. Examples ofsurfactants suitable for the practice of the present invention include,but are not limited to: alkoxylated tertiary etheramines (such as TOMAHE-Series surfactants); alkoxylated quaternary etheramine (such as TOMAHQ-Series surfactant); alkoxylated etheramine oxides (such as TOMAHAO-Series surfactant); alkoxylated tertiary amine oxides (such as AROMOXseries surfactants); alkoxylated tertiary amine surfactants (such as theETHOMEEN T and C series surfactants); alkoxylated quaternary amines(such as the ETHOQUAD T and C series surfactants); alkyl sulfates, alkylether sulfates and alkyl aryl ether sulfates (such as the WITCOLATEseries surfactants); alkyl sulfonates, alkyl ether sulfonates and alkylaryl ether sulfonates (such as the WITCONATE series surfactants);alkoxylated phosphate esters and diesters (such as the PHOSPHOLAN seriessurfactants); alkyl polysaccharides (such as the AGRIMUL PG seriessurfactants); alkoxylated alcohols (such as the BRIJ or HETOXOL seriessurfactants); and mixtures thereof.

Anti-packing agents facilitate redispersion of microcapsules uponagitation of a formulation in which the microcapsules have settled. Amicrocrystalline cellulose material such as LATTICE from FMC iseffective as an anti-packing agent. Other suitable anti-packing agentsare, for example, clay, silicon dioxide, insoluble starch particles, andinsoluble metal oxides (e.g. aluminum oxide or iron oxide). Anti-packingagents which change the pH of the dispersion are preferably avoided, forat least some embodiments.

Drift control agents suitable for the practice of the present inventionare known to those skilled in the art and include the commercialproducts GARDIAN, GARDIAN PLUS, DRI-GARD, PRO-ONE XL ARRAY, COMPADRE,IN-PLACE, BRONC MAX EDT, EDT CONCENTRATE, COVERAGE and BRONC Plus DryEDT.

The formulated microcapsule dispersions of the present invention arepreferably easily redispersed, so as to avoid problems associated withapplication (e.g., clogging a spray tank). Dispersability may bemeasured by the Nessler tube test, wherein Nessler tubes are filled with95 ml of water, then 5 ml of the test formulation is added by syringe.The tube is stoppered, and inverted ten times to mix. It is then placedin a rack, standing vertically, for 18 hours at 20° C. The tubes areremoved and smoothly inverted every five seconds until the bottom of thetube is free of material. The number of inversions required to remix thesettled material from the formulation is recorded. Preferably, thedispersions of the present invention are redispersed with less thanabout 100 inversions as measured by a Nessler tube test. Morepreferably, less than about 20 inversions are required for redispersion.

The pH of the formulated microcapsule dispersion may preferably rangefrom about 4 to about 9, in order to minimize eye irritation of thosepersons who may come into contact with the formulation in the course ofhandling or application to crops. However, if components of a formulateddispersion are sensitive to pH, such as for example the blocking agent,buffers such as disodium phosphate may be used to hold the pH in a rangewithin which the components are most effective. Additionally, a pHbuffer such as citric acid monohydrate may be particularly useful insome systems during the preparation of microcapsules, to maximize theeffectiveness of a protective colloid such as SOKALAN CP9.

Other useful additives include, for example, biocides or preservatives(e.g., PROXEL, commercially available from Avecia), antifreeze agents(such as glycerol, sorbitol, or urea), and antifoam agents (such asAntifoam SE23 from Wacker Silicones Corp.).

Controlling Plant Growth with Microcapsule Dispersions

The microcapsule dispersions disclosed herein are useful ascontrolled-release herbicides or concentrates thereof. Therefore, thepresent invention is also directed to a method of applying a dispersionof the microencapsulated herbicides for controlling plant growth. Insome embodiments, herein, the dispersion of herbicidal microcapsules isapplied to the soil, before planting the crop plants or after planting,but preemergent to the crop plants.

A microcapsule dispersion may be applied to a field according topractices known to those skilled in the art. The microcapsules arepreferably applied as a controlled release delivery system for anagricultural chemical (e.g., acetanilide herbicide) or blend ofagricultural chemicals contained therein. Because the mean releasecharacteristics of a population of microcapsules of the presentinvention are adjustable, the timing of release initiation (or increaserelease) can be controlled thereby giving both commercially acceptableweed control and a commercially acceptable rate of crop injury.

When blended for end use on an agricultural field, the dispersion ofherbicide-containing microcapsules prior to dilution by the end user maybe, for example, less than about 62.5 weight percent microcapsules, oralternatively, less than about 55 weight percent herbicide or otheractive. If the dispersion is too concentrated with respect tomicrocapsules, the viscosity of the dispersion may be too high to pumpand also may be too high to easily redisperse if settling has occurredduring storage. It is for these reasons that the dispersion preferablyhas a viscosity of less than about 400 cps, as describe above.

The microcapsule dispersions may be as dilute with respect tomicrocapsule weight percent as is preferred by the user, constrainedmainly by the economics of storing and transporting the additional waterfor dilution and by possible adjustment of the additive package tomaintain a stable dispersion. Typically, the dispersion is at leastabout 25 weight percent herbicidal active (about 30 weight percentmicrocapsules) for these reasons. These concentrations are usefulcompositions for the storage and transport of the dispersions.

For a stand-alone (i.e., in the absence of a co-herbicide) applicationof the microcapsules of the present invention, the dispersion ispreferably diluted with water to form an application mixture prior toapplication. Typically, no additional additives are required to placethe dispersion in a useful condition for application as a result ofdilution. The optimal concentration of a diluted dispersion is dependentin part on the method and equipment which is used to apply theherbicide.

The effective amount of microcapsules to be applied to an agriculturalfield is dependent upon the identity of the encapsulated herbicide, therelease rate of the microcapsules, the crop to be treated, andenvironmental conditions, especially soil type and moisture. Generally,application rates of herbicides, such as, for example, acetochlor, areon the order of about 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10kilograms of herbicide per hectare, or ranges thereof, such as from 0.5to 10 kilograms per hectare, from 0.5 to 10 kilograms per hectare, from0.5 to 5 kilograms per hectare, or from 1 to 5 kilograms per hectare. Insome embodiments, an application rate for sorghum, rice and wheat offrom about 0.85 to about 1 kilograms per hectare is preferred. For othercrops, e.g., corn, peanuts, potatoes, soybeans, canola, alfalfa,sugarcane, sugarbeets, peanuts, field beans, sunflowers and cotton, anapplication rate of about 1.1 to about 1.4 kilograms per hectare ispreferred.

Application mixtures of the dispersions of the microencapsulatedacetamide herbicides are preferably applied to an agricultural fieldwithin a selected timeframe of crop plant development. In someembodiments of the present invention, as described above, the dispersionof the microencapsulated herbicides, optionally including one or moreco-herbicides, is applied to a field from 1-40 days prior to planting ofthe crop plant and/or preemegence (i.e., from planting of the crop plantup to, but not including, emergence or cracking) in order to providecontrol of newly emerging monocots and small seeded dicot specieswithout significant crop damage. In other embodiments, a particulatemicroencapsulated acetamide herbicide composition comprising a firstparticulate microencapsulated acetamide herbicide and a secondmicroencapsulated acetamide herbicide, optionally further comprising oneor more co-herbicides, is applied to a field from 1-40 days prior tocrop planting and/or preemegence.

Application mixtures of the aqueous dispersions of herbicidalmicrocapsules of the present invention are useful for controlling a widevariety of weeds, i.e., plants that are considered to be a nuisance or acompetitor of commercially important crop plants, such as corn, soybean,cotton, etc. In some embodiments, the microcapsules of the presentinvention are applied before the weeds emerge (i.e., preemergenceapplication). Examples of weeds that may be controlled according to themethod of the present invention include, but are not limited to, MeadowFoxtail (Alopecurus pratensis) and other weed species with theAlopecurus genus, Common Barnyard Grass (Echinochloa crus-galli) andother weed species within the Echinochloa genus, crabgrasses within thegenus Digitaria, White Clover (Trifolium repens), Lambsquarters(Chenopodium berlandieri), Redroot Pigweed (Amaranthus retroflexus) andother weed species within the Amaranthus genus, Common Purslane(Portulaca oleracea) and other weed species in the Portulaca genus,Chenopodium album and other Chenopodium spp., Setaria lutescens andother Setaria spp., Solanum nigrum and other Solanum spp., Loliummultiflorum and other Lolium spp., Brachiaria platyphylla and otherBrachiaria spp., Sorghum halepense and other Sorghum spp., ConyzaCanadensis and other Conyza spp., and Eleusine indica. In someembodiments, the weeds comprise one or more glyphosate-resistantspecies, 2,4-D-resistant species, dicamba-resistant species and/or ALSinhibitor herbicide-resistant species. In some embodiments, theglyphosate-resistant weed species is selected from the group consistingof Amaranthus palmeri, Amaranthus rudis, Ambrosia artemisiifolia,Ambrosia trifida, Conyza bonariensis, Conyza canadensis, Digitariainsularis, Echinochloa colona, Eleusine indica, Euphorbia heterophylla,Lolium multiflorum, Lolium rigidum, Plantago lancelata, Sorghumhalepense, and Urochloa panicoides.

As used herein transgenic glyphosate-tolerant corn, soybean, cotton,etc. plants includes plants grown from the seed of any corn, soybean,cotton, etc. event that provides glyphosate tolerance andglyphosate-tolerant progeny thereof.

Such glyphosate-tolerant events include, without limitation, those thatconfer glyphosate tolerance by the insertion or introduction, into thegenome of the plant, the capacity to express various native and variantplant or bacterial EPSPS enzymes by any genetic engineering means knownin the art for introducing transforming DNA segments into plants toconfer glyphosate resistance as well as glyphosate-tolerant cottonevents that confer glyphosate tolerance by other means such as describedin U.S. Pat. Nos. 5,463,175 and 6,448,476 and International PublicationNos. WO 2002/36782, WO 2003/092360 and WO 2005/012515.

Non-limiting examples of transgenic glyphosate-tolerant cotton eventsinclude the glyphosate-tolerant (ROUNDUP READY) cotton event designated1445 and described in U.S. Pat. No. 6,740,488. Of particular interest inthe practice of one embodiment of the present invention are methods forweed control in a crop of transgenic glyphosate-tolerant cotton plantsin which glyphosate resistance is conferred in a manner that allowslater stage application of glyphosate herbicides without incurringsignificant glyphosate-mediated reproductive injury. Non-limitingexamples of such transgenic glyphosate-tolerant cotton plants includethose grown from the seed of the glyphosate-tolerant (ROUNDUP READY)FLEX cotton event (designated MON 88913 and having representative seeddeposited with American Type Culture Collection (ATCC) with AccessionNo. PTA-4854) and similar glyphosate-tolerant cotton events and progenythereof as described in International Publication No. WO 2004/072235.Glyphosate-tolerant (ROUNDUP READY FLEX) cotton event MON 88913 andsimilar glyphosate-tolerant cotton events may be characterized in thatthe genome comprises one or more DNA molecules selected from the groupconsisting of SEQ ID NO:1, SEQ ID NO:2, SEQ ID NO:3, and SEQ ID NO:4; orthe genome in a DNA amplification method produces an amplicon comprisingSEQ ID NO:1 or SEQ ID NO:2; or the transgenic glyphosate-tolerant cottonplants comprise a glyphosate tolerant trait that is genetically linkedto a complement of a marker polynucleic acid, and the marker polynucleicacid molecule is homologous or complementary to a DNA molecule selectedfrom the group consisting of SEQ ID NO:1 and SEQ ID NO:2 as described inInternational Publication No. WO 2004/072235, the entire contents ofwhich are incorporated herein by reference. A sequence listingcontaining each of SEQ ID NOS: 1, 2, 3, and 4 as disclosed inInternational Publication No. WO 2004/072235 is contained herein. Thesesequences are listed as SEQ ID NOS: 1, 2, 3, and 4, respectively.

As noted above, the glyphosate-tolerant (ROUNDUP READY FLEX) cottonevent MON 88913 allows for over-the-top application of glyphosateherbicides at advanced stages of plant development without incurringsignificant glyphosate-mediated reproductive injury (e.g., asquantified, for example, by flower pollen shed and/or lint yield). Ascompared to the previous commercial glyphosate-tolerant (ROUNDUP READY)cotton event designated 1445, glyphosate-tolerant (ROUNDUP READY FLEX)cotton event MON 88913 is particularly advantageous in allowing foliarapplication of glyphosate herbicide for weed control at a developmentalage characterized by at least five leaf nodes present on a cotton plantof the crop. As used herein, a node having a leaf branch is referred toas a leaf node in accordance with the conventional node method used inassessing cotton plant developmental age. Furthermore, cotyledons areleaves originally contained in the seed and are not considered as plantleaves or nodes for purposes of determination of the stage of cottondevelopment. That is, as generally accepted by those skilled in the artand as used herein, the stem point of cotyledon attachment is referencedas Node 0. The fifth and subsequent leaf nodes are typically the firstreproductive (i.e., fruiting) branches and may develop a fruiting budand associated leaf. A leaf node having a reproductive branch may bereferred as a reproductive node. Cotton plants can develop as many asabout 25 leaf nodes, with nodes 5-25 potentially developing intoreproductive nodes. In practicing weed control in a crop of transgenicglyphosate-tolerant cotton grown from seed of glyphosate-tolerant(ROUNDUP READY FLEX) cotton event MON 88913 or similar cotton events andprogeny thereof, glyphosate herbicidal formulations can be appliedover-the-top of the crop at more advanced developmental agescharacterized, for example, by six, ten, twelve, fourteen or more leafnodes present on a cotton plant of the crop and up to and includinglayby without incurring significant glyphosate-mediated reproductiveinjury to the crop. Herbicidal glyphosate formulation may be appliedover-the-top of the cotton crop at various intervals of advanceddevelopment, characterized, for example, by six or more leaf nodes andno more than ten, twelve, fourteen, sixteen, eighteen, twenty ortwenty-five leaf nodes on a cotton plant of the crop.

In some embodiments as described previously, the herbicidalmicrocapsules of the present invention, including blends of a first andsecond particulate microencapsulated acetamide herbicide, can bedispersed in combination with one or more co-herbicides in an aqueousconcentrate or spray application tank mix, such as a co-herbicideselected from ACCase inhibitors (such as aryloxyphenoxypropionics),enolpyruvyl shikimate-3-phosphate synthaste (EPSPS) inhibitor(glyphosate), glutamine synthetase inhibitor (glufosinate), syntheticauxins (such as aromatic acid, phenoxy and pyridine herbicides),photosystem II (PS II) inhibitors (such as ureas and triazines), ALS orAHAS inhibitors (such as sulfonyl ureas, triazolopyrimidines andimidazolinones), photosystem I (PS I) inhibitors (such as quaternaryammonium herbicides), protoporphyrinogen oxidase (PPO) inhibitors (suchas diphenyl ethers, phenyl pyrazoles, aryl triazones and oxadiazoles),mitosis inhibitors (such as anilide, amide, certain organophosphorus andcarbanilate herbicides), cellulose inhibitors (such as nitrile andoxazole herbicides), oxidative phosphorylation uncouplers,dihydropteroate synthase inhibitors, fatty acid and lipid biosynthesisinhibitors (such as thiocarbamate and certain organophosphorusherbicides), auxin transport inhibitors (such as amide and ureaherbicides) and carotenoid biosynthesis inhibitors (such asisoxazolidinone, benzoylcyclohexanedione and benzoylpyrazoleherbicides), salts and esters thereof, and mixtures thereof. Applicationmixtures of the co-herbicide formulations can likewise be prepared. Aweight ratio of acetamide to co-herbicide of from 10:1 to 1:10 or from5:1 to 1:5 is preferred. In some embodiments of the present invention,the one or more co-herbicides are not encapsulated.

Where an herbicide is referenced generically herein by name, unlessotherwise restricted, that herbicide includes all commercially availableforms known in the art such as salts, esters, free acids and free bases,as well as stereoisomers thereof. For example, where the herbicide name“glyphosate” is used, glyphosate acid, salts and esters are within thescope thereof.

An EPSPS herbicide is glyphosate or a salt or ester thereof. A glutaminesynthetase herbicide is glufosinate or glufosinate-P, or a salt or andester thereof.

ACCase inhibitors include, for example, alloxydim, butroxydim,clethodim, cycloxydim, pinoxaden, sethoxydim, tepraloxydim andtralkoxydim, salts and esters thereof, and mixtures thereof. Anothergroup of acetyl CoA carboxylase inhibitors include chlorazifop,clodinafop, clofop, cyhalofop, diclofop, diclofop-methyl, fenoxaprop,fenthiaprop, fluazifop, haloxyfop, isoxapyrifop, metamifop,propaquizafop, quizalofop and trifop, salts and esters thereof, andmixtures thereof. Acetyl CoA carboxylase inhibitors also includemixtures of one or more “dims” and one or more “fops”, salts and estersthereof.

Synthetic auxin herbicides include, for example, 2,4-D, 2,4-DB,dichloroprop, MCPA, MCPB, aminopyralid, clopyralid, fluroxypyr,triclopyr, diclopyr, mecoprop, dicamba, picloram and quinclorac, saltsand esters thereof, and mixtures thereof.

PS II inhibitors include, for example, ametryn, amicarbazone, atrazine,bentazon, bromacil, bromoxynil, chlorotoluron, cyanazine, desmedipham,desmetryn, dimefuron, diuron, fluometuron, hexazinone, ioxynil,isoproturon, linuron, metamitron, methibenzuron, metoxuron, metribuzin,monolinuron, phenmedipham, prometon, prometryn, propanil, pyrazon,pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil,terbumeton, terbuthylazine and trietazine, salts and esters thereof, andmixtures thereof.

ALS and AHAS inhibitors include, for example, amidosulfuron,azimsulfruon, bensulfuron-methyl, bispyribac-sodium, chlorimuron-ethyl,chlorsulfuron, cinosulfuron, cloransulam-methyl, cyclosulfamuron,diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron,florazulam, flucarbazone, flucetosulfuron, flumetsulam,flupyrsulfuron-methyl, foramsulfuron, halosulfuron-methyl,imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr,imazosulfuron, iodosulfuron, metsulfuron-methyl, nicosulfuron,penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, prosulfuron,pyrazosulfuron-ethyl, pyribenzoxim, pyrithiobac, rimsulfuron,sulfometuron-methyl, sulfosulfuron, thiencarbazone,thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuronand triflusulfuron-methyl, salts and esters thereof, and mixturesthereof.

Mitosis inhibitors include anilofos, benefin, DCPA, dithiopyr,ethalfluralin, flufenacet, mefenacet, oryzalin, pendimethalin, thiazopyrand trifluralin, salts and esters thereof, and mixtures thereof.

PPO inhibitors include, for example, acifluorfen, azafenidin, bifenox,butafenacil, carfentrazone-ethyl, flufenpyr-ethyl, flumiclorac,flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluthiacet-methyl,fomesafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen,pyraflufen-ethyl, saflufenacil and sulfentrazone, salts and estersthereof, and mixtures thereof.

Carotenoid biosynthesis inhibitors include, for example, aclonifen,amitrole, beflubutamid, benzofenap, clomazone, diflufenican, fluridone,flurochloridone, flurtamone, isoxaflutole, mesotrione, norflurazon,picolinafen, pyrazolynate, pyrazoxyfen, sulcotrione, tembotrione andtopramezone, salts and esters thereof, and mixtures thereof.

PS I inhibitors include diquat and paraquat, salts and esters thereof,and mixtures thereof.

Cellulose inhibitors include dichlobenil and isoxaben.

An oxidative phosphorylation uncoupler is dinoterb, and esters thereof.

Auxin transport inhibitors include diflufenzopyr and naptalam, salts andesters thereof, and mixtures thereof.

A dihydropteroate synthase inhibitor is asulam and salts thereof.

Fatty acid and lipid biosynthesis inhibitors include bensulide,butylate, cycloate, EPIC, esprocarb, molinate, pebulate, prosulfocarb,thiobencarb, triallate and vernolate, salts and esters thereof, andmixtures thereof.

Some preferred co-herbicides include flumioxazin, fluometuron, diuron,sulfentrazone, fomesafen, metribuzen, saflufenacil, thiencarbazone,mesotrione, atrazine, isoxaflutole, 2,4-D, dicamba and glyphosate, saltsand esters thereof, racemic mixtures and resolved isomers thereof, andmixtures thereof.

In some embodiments of the present invention, the co-herbicide isflumioxazin and the crop plant is cotton or soy; the co-herbicide isfomesafen and the crop plant is cotton or soy; the co-herbicide ismetribuzen and the crop plant is soy; the co-herbicide is saflufenaciland the crop plant is cotton or soy; the co-herbicide is thiencarbazoneand the crop plant is corn; the co-herbicide is mesotrione and the cropplant is corn, cotton or soy; the co-herbicide is atrazine and the cropplant is corn; the co-herbicide is isoxaflutole and the crop plant iscorn, cotton or soy; or the co-herbicide is 2,4-D or dicamba and thecrop plant is not limited, but can be, for example, corn, peanuts,potatoes, soybeans, canola, alfalfa, sugarcane, sugarbeets, peanuts,grain sorghum (milo), field beans, rice, sunflowers, wheat or cotton.

In some embodiments the herbicidal microcapsules of the presentinvention can be dispersed with two co-herbicides to form a three-wayherbicidal composition. The compositions can be concentrate compositionsor application mixtures. A weight ratio of acetamide to totalco-herbicide of from 10:1 to 1:10 or from 5:1 to 1:5 is preferred. Atable of co-herbicide combinations within the scope of the presentinvention is provided below where “Comb” is a combination referencenumber, “Gly or glu” refers to glyphosate or glufosinate, and “1stco-herb” and “2nd co-herb” refer to the first and secondnon-encapsulated co-herbicide classes that are combined with theencapsulated acetamide (e.g. acetanilide).

Comb 1st co-herb 2nd co-herb 1 Gly or glu ACCase 2 Gly or glu Auxin 3Gly or glu PS II 4 Gly or glu ALS 5 Gly or glu Mitosis 6 Gly or glu PPO7 Gly or glu Carotenoid 8 ACCase Auxin 9 ACCase PS II 10 ACCase ALS 11ACCase Mitosis 12 ACCase PPO 13 ACCase Carotenoid 14 Auxin PS II 15Auxin ALS 16 Auxin Mitosis 17 Auxin PPO 18 Auxin Carotenoid 19 PS II ALS20 PS II Mitosis 21 PS II PPO 22 PS II Carotenoid 23 ALS Mitosis 24 ALSPPO 25 ALS Carotenoid 26 Mitosis PPO 27 Mitosis Carotenoid 28 PPOCarotenoid

In some embodiments, the encapsulated acetamides are combined in anaqueous application mixture with an auxin herbicide and anorganophosphate herbicide, or salt or ester thereof. In someembodiments, the encapsulated acetamide herbicide is selected fromacetochlor, metolachlor, S-metolachlor, dimethenamide anddimethenamide-P salts and esters thereof, the first co-herbicide isselected from dicamba and 2,4-D, salts and esters thereof, and thesecond co-herbicide is selected from glyphosate, glufosinate andglufosinate-P, salts and esters thereof. Examples include: encapsulatedacetochlor, dicamba and glyphosate; encapsulated metolachlor and/orS-metolachlor, dicamba and glyphosate; encapsulated dimethenamid and/ordimethenamid-P, dicamba and glyphosate; encapsulated acetochlor, 2,4-Dand glyphosate; encapsulated metolachlor and/or S-metolachlor, 2,4-D andglyphosate; encapsulated dimethenamid and/or dimethenamid-P, 2,4-D andglyphosate; encapsulated acetochlor, dicamba and glufosinate and/orglufosinate-P; encapsulated metolachlor and/or S-metolachlor, dicambaand glufosinate and/or glufosinate-P; encapsulated dimethenamid and/ordimethenamid-P, dicamba and glufosinate and/or glufosinate-P;encapsulated acetochlor, 2,4-D and glufosinate and/or glufosinate-P;encapsulated metolachlor and/or S-metolachlor, 2,4-D and glufosinateand/or glufosinate-P; and encapsulated dimethenamid and/ordimethenamid-P, 2,4-D and glufosinate and/or glufosinate-P.

In some preferred embodiments the first co-herbicide is anorganophosphorus herbicide and the second co-herbicide is a PS IIherbicide. Examples include glyphosate and atrazine, metribuzen orfluometuron.

In some other preferred embodiments, the first co-herbicide is anorganophosphorus herbicide and the second co-herbicide is a PPOherbicide. Examples include glyphosate and flumioxazin, fomesafen,lactofen, sulfentrazone, oxyfluorfen or saflufenacil.

In other preferred embodiments the first co-herbicide is a PS IIherbicide and the second co-herbicide is a PPO herbicide. Examplesinclude atrazine, metribuzen or fluometuron as PS II herbicides incombination with flumioxazin, fomesafen, lactofen, sulfentrazone,oxyfluorfen or saflufenacil as PPO herbicides.

In other preferred embodiments, the present microcapsules are used inthe preparation of an aqueous concentrate composition or tank mixcomprising glyphosate or a salt thereof (e.g., the potassium ormonoethanolammonium salt). In such a tank mix, a percent by weightacetamide from about 5% to about 0.1% a.i. and from about 3% by weightto about 0.25% a.e. by weight is preferred. Such an aqueous compositionis particularly useful for burndown applications prior to crop emergenceto control glyphosate susceptible plants and several commerciallyimportant weeds that have been reported to be glyphosate resistant,including, for example, palmer amaranth (Amaranthus palmeri), waterhemp(Amaranthus rudis), common ragweed (Ambrosia artemisiifolia), giantragweed (Ambrosia trifida), hairy fleaane (Conyza bonariensis),horseweed (Conyza canadensis), sourgrass (Digitaria insularis),junglerice (Echinochloa colona), goosegrass (Eleusine indica), wildpoinsettia (Euphorbia heterophylla), Italian ryegrass (Loliummultiflorum), rigid ryegrass (Lolium rigidum), buckhorm plantain(Plantago Lancelata), Johnsongrass (Sorghum halepense), andliverseedgrass (Urochloa panicoides).

As used throughout this specification, the expression “predominantlycomprises” means more than 50%, preferably at least about 75%, and morepreferably at least about 90% by weight of the component is made up ofthe specified compound(s).

EXAMPLES

The following non-limiting Examples are provided to further illustratethe present invention. The materials shown in the following Table wereused in the following Examples. Throughout the Examples, thesecomponents are referred to by the term stated in the Reference column.

Material Function Reference Supplier Acetochlor Herbicide AcetochlorMonsanto Furilazole Safener Monsanto n-Pentadecane Internal Phase NORPAR15 Exxon Solvent Mobil (dilutent) Isoparaffinic Internal Phase ISOPAR VExxon hydrocarbon Solvent Mobil (approximate MW 234) (dilutent)Isoparaffinic Internal Phase ISOPAR L Exxon hydrocarbon Solvent Mobil(approximate MW 163) (dilutent) Dearomatized Internal Phase EXXSOL Exxonhydrocarbon Solvent D-130 Mobil (approximate MW 229) (dilutent)Dearomatized Internal Phase EXXSOL Exxon hydrocarbon Solvent D-110 Mobil(approximate MW 200) (dilutent) Triethylenetetramine Amine shell wallTETA Huntsman 50% solution component Chemical Meta-Xylylenediamine Amineshell wall XDA 50% solution component Desmodur N3200 Triisocyanate DESN3200 Bayer Trimer of shell wall hexamethylene-1,6- componentdiisocyanate Desmodur W Diisocyanate DES W Bayer 4,4′-diisocyanato-shell wall dicyclohexyl methane component 85% by weight trimer Blend ofDES MISTA- Monsanto of hexamethylene- N3200 and FLEX 1,6-diisocyanate:DES W 15% by weight 4,4′- diisocyanato- dicyclohexyl methane WaterExternal Phase Water Solvent Ammonium caseinate Dispersant AmmoniumAmerican caseinate Casein Company Glycerin Glycerin Cargill Maleicacid-olefin surfactant SOKALAN BASF copolymer, 25% CP9 solution CitricAcid, 50% pH adjustment Acid ADM solution Invalon DAM Dispersant InvalonHuntsman Naphthalene Chemical formaldehyde condensate sulfonate KelzanCC Thickener Kelzan CC Kelco Proxel GXL Preservative Proxel GXL AveciaNAOH, 20% solution pH adjustment Caustic Dow Chemical Antifoam SE23Antifoam Antifoam Wacker Silicone Na₂HPO₄ Buffer Buffer ICL Per-formance Products

The herbicidal effectiveness data set forth herein report crop damageand weed inhibition as a phytotoxicity percentage following a standardprocedure in the art which reflects a visual assessment of plantmortality and growth reduction by comparison with untreated plants, madeby technicians specially trained to make and record such observations.In all cases, a single technician makes all assessments of percentinhibition within any one experiment or trial.

The selection of application rates that are biologically effective for aspecific acetamide herbicide is within the skill of the ordinaryagricultural scientist. Those of skill in the art will likewiserecognize that individual plant conditions, weather and growingconditions, as well as the specific exogenous chemical and formulationthereof selected, will affect the efficacy on weeds and associated cropinjury achieved in practicing this invention. Useful application ratesfor the acetamide herbicides employed can depend upon all of the abovefactors. With respect to the use of the method of this invention, muchinformation is known about appropriate acetamide application rates. Overfour decades of acetamide use and published studies relating to such usehave provided abundant information from which a weed controlpractitioner can select acetamide application rates that areherbicidally effective on particular species at particular growth stagesin particular environmental conditions.

Effectiveness in greenhouse tests, usually at exogenous chemical rateslower than those normally effective in the field, is a proven indicatorof consistency of field performance at normal use rates. However, eventhe most promising composition sometimes fails to exhibit enhancedperformance in individual greenhouse tests. As illustrated in theExamples herein, a pattern of enhancement emerges over a series ofgreenhouse tests; when such a pattern is identified this is strongevidence of biological enhancement that will be useful in the field.

The compositions of the present invention can be applied to soil orplants by spraying, using any conventional means for spraying liquids,such as spray nozzles, atomizers, or the like. Compositions of thepresent invention can be used in precision farming techniques, in whichapparatus is employed to vary the amount of exogenous chemical appliedto different parts of a field, depending on variables such as theparticular plant species present, soil composition, and the like. In oneembodiment of such techniques, a global positioning system operated withthe spraying apparatus can be used to apply the desired amount of thecomposition to different parts of a field.

The composition, at the time of application to soil or plants, ispreferably dilute enough to be readily sprayed using standardagricultural spray equipment. Preferred application rates for thepresent invention vary depending upon a number of factors, including thetype and concentration of active ingredient and the plant speciesinvolved. Selection of appropriate rates of application is within thecapability of one skilled in the art. Useful rates for applying anaqueous application mixture to a field can range from about 50 to about1,000 liters per hectare (L/ha) by spray application. The preferredapplication rates for aqueous application mixtures are in the range fromabout 100 to about 300 L/ha.

Damage to the foliage of a crop plant may cause the plant to be stuntedor otherwise reduce the yield of the desired agricultural commodity.Thus, it is important that a herbicidal composition not be applied insuch a manner as to excessively injure and interrupt the normalfunctioning of the plant tissue. However, some limited degree of localinjury can be insignificant and commercially acceptable.

A large number of compositions of the invention are illustrated in theexamples that follow. Many concentrate acetamide compositions haveprovided sufficient herbicidal effectiveness in greenhouse tests towarrant field testing on a wide variety of weed species under a varietyof application conditions.

Some of the experiments were carried out in a greenhouse. The herbicidalcompositions were applied using a research track sprayer. The dilutionof the dispersion of herbicidal microcapsules were varied in orderachieve different concentrations of active applied.

Example 1. Preparation of Aqueous Dispersions of MicroencapsulatedAcetochlor

Aqueous dispersions of microencapsulated acetochlor were preparedaccording to the protocol described in this example. The aqueousdispersions were prepared using a method that resulted in microcapsuleshaving a mean diameter greater than those found in DEGREE, acommercially available microencapsulated herbicidal product containingabout 42% by weight acetochlor, available from Monsanto Company. Themicrocapsules in DEGREE have a mean diameter of about 2.5 μm. The testformulations resulted in aqueous dispersions of microcapsules havingmean diameters significantly greater, such as about 5 μm to about 13 μm.Field studies indicated that the aqueous dispersions of herbicidalmicrocapsules having larger mean diameters exhibited improved cropsafety when tested on soybean and cotton compared to DEGREE and alsocompared to HARNESS, a commercially available herbicidal productcontaining emulsified concentrate of unencapsulated acetochlor, alsoavailable from Monsanto Company.

The internal phases were prepared to contain the components and amountsshown in the following table. The percentages indicate the approximateweight percentage of each component in the aqueous dispersion.

TABLE Internal Phase Components Acetochlor NORPAR 15 MISTAFLEX Form. (g)(%) (g) (%) (g) (%) 5291 447.25 43.19 23.56 2.35 30.84 3.07 5297 894.2143.19 46.99 2.35 61.53 3.07 5295 841.2 40.63 107.01 5.00 61.73 3.07

To prepare the internal phase of formulations 5291, 5297, and 5295,acetochlor was charged to the mixing vessels in the amounts shown in theabove internal phase components table. Next, NORPAR 15 was charged tothe mixing vessels, followed by the MISTAFLEX blend of DES N3200 and DESW polyisocyanates. The solution was agitated to obtain a clearhomogenous solution. The solution may be sealed within the mixing vesseland stored until needed. Prior to use, the mixture was heated to 50° C.in an oven.

The external aqueous phases were prepared containing the components andamounts shown in the following table:

TABLE External Phase Components Weight of Components in grams AmmoniumSOKALAN Form. Water Caseinate Glycerin CP9 Acid 5291 278.2 0.45 81.123.0 1.64 5297 556.61 0.98 162.28 46.04 3.09 5295 556.32 0.93 162.2746.63 3.23

To prepare the external phase of formulations 5291, 5297, and 5295,mixing vessels were charged with water in the amounts shown in the aboveexternal phase components table, and the remaining components were addedin the order shown in the above table. The solution was agitated toobtain a clear homogenous solution. The solution may be sealed withinthe mixing vessel and stored until needed. Prior to use, the mixture washeated to 50° C. in an oven.

The interfacial polymerization medium was prepared by first charging theexternal phase to a Waring blender cup that has been preheated to 50° C.The commercial Waring blender (Waring Products Division, DynamicsCorporation of America, New Hartford, Conn., Blender 700) was poweredthrough a 0 to 120 volt variable autotransformer. The blender mix speedwas varied by controlling power to the blender as shown below in theemulsification parameters table. The internal phase was added to theexternal phase over a 16 second interval and blending was continued toobtain an emulsion.

TABLE Emulsification Parameters Form. Voltage (V) Power (%) Duration (s)5297 120 40 120 5295 120 40 —

To initiate polymerization and encapsulation of the internal phase, a50% by weight solution of TETA was added to the emulsion to the amountsshown in the following Amine Table over a period of about 5 seconds. Theblender speed is then reduced to a speed which just produces a vortexfor approximately five to fifteen minutes. The emulsion was thentransferred to a hot plate and stirred. The reaction vessel is coveredand maintained at about 50° C. for approximately two hours which hasbeen found is sufficient time for the isocyanate to react essentiallycompletely.

TABLE Amine TETA, 50% by weight solution Form. (g) (%) 5291 14.14 1.39%5297 27.72 1.39% 5295 27.92 1.39%

The capsule slurry is then allowed to cool to close to room temperature.The components shown in the stabilizer components table with theexception of the buffer are previously premixed with a high speed mixer(Waring Blender or Cowles Dissolver). The resulting stabilizer premix isthen added to the capsule slurry to stabilize the dispersion ofmicrocapsules. Finally the buffer is added and the mixture is stirredfor at least 15 minutes until visually homogeneous.

Due to variations in the blender design and other uncontrollablevariables, it was found to be difficult to correlate blender speed andparticle size accurately. In consequence, some samples were discardedbecause they did not have the desired size. Samples were chosen forevaluation based on their measured particle size.

TABLE Stabilizer Components Form. Weight of Components in grams InvalonGlycerin Kelzan CC 5291 58.41 39.2 0.53 5297 116.83 78.37 1.04 5295116.83 78.37 1.04 Proxel GXL Caustic Antifoam Buffer 5291 0.53 0.23 0.011.18 5297 1.04 0.354 0.01 2.38 5295 1.04 0.354 0.01 2.38

Formulations 5291, 5297, and 5295 were stabilized aqueous dispersions ofmicrocapsules containing acetochlor at an approximate activeconcentration of 42.5% ai by weight (which approximately the same activeconcentration as DEGREE).

Each formulation was prepared to have an excess molar equivalents ratioof amine molar equivalents to isocyanate molar equivalents and herbicideto shell wall component ratios. TETA has an approximate equivalentweight of 36.6 g/mol. DES N3200 has an approximate equivalent weight of183 g/mol (theoretical equivalent weight is 159.53 g/mol). DES W has anapproximate equivalent weight of 132 g/mol. Formulation 5295 wasprepared with an excess of internal phase solvent (diluent), NORPAR 15.The formulations had the following weight ratios:

TABLE Formulation Characteristics Ratio of Ratio of Molar Herbicide toHerbicide to equivalents Shell Wall Internal Phase Form. ratioComponents Solvent 5291 1.08:1 9.94:1 18.98:1 5297 1.06:1 10.02:1 19.03:1 5295 1.06:1 9.38:1  7.86:1

The blender speed was controlled to produce an increased microcapsulesize compared to the microcapsules in DEGREE, which is about 2.5 μm. Theparticle size parameters were measured using a Beckman Coulter LSParticle Size Analyzer. The mean particle sizes and standard deviationsof the microcapsules in the slurry for each formulation are shown in thefollowing table:

TABLE Particle Size Parameters Mean Particle size Standard DeviationForm. (μm) (μm) 5291 5.57 3.99 5297 13.97 8.5 5295 12.70 7.85

Example 2. Preparation of Aqueous Dispersions of MicroencapsulatedAcetochlor

Aqueous dispersions of two microencapsulated acetochlor formulations,referenced as 410P9M and 403U7N, were prepared according to the methodof Example 1. Composition 410P9M comprised the weight percent amountsshown in the following table.

TABLE 410P9M Component Weight Percent Internal Phase Acetochlor (95.4%)34.59 (33.0) NORPAR 15  1.78 MISTAFLEX H9915  2.52 External PhaseGlycerin  9.66 SOKALAN CP9 (25%)  2.85 (0.71) Ammonium Caseinate  0.057Citric Acid  0.21 Water 34.81 TETA, 50% solution  1.28 (0.64) StabilizerInvalon (40%)  7.15 (2.86) Kelzan CC  0.064 Antifoam  0.001 Glycerin 4.80 Proxel GXL  0.064 Caustic  0.022 Buffer  0.14

Composition 403U7N was prepared from similar components, but wherein theacetochlor loading and ratio of amine to isocyanate was altered toprovide higher acetochlor loading and larger particle size. Composition403U7N comprised the weight percent amounts shown in the followingtable.

TABLE 403U7N Component Weight Percent Internal Phase Acetochlor (95.4%)42.95 (41.0) NORPAR 15  5.00 MISTAFLEX H9915  3.08 External PhaseGlycerin  7.73 SOKALAN CP9 (25%)  2.28 (0.57) Ammonium Caseinate  0.046Citric Acid  0.164 Water 27.85 TETA, 50% solution  1.37 (0.69)Stabilizer Invalon (40%)  5.56 (2.22) Kelzan CC  0.05 Antifoam  0.001Glycerin  3.73 Proxel GXL  0.05 Caustic  0.017 Buffer  0.14

The particle size parameters for compositions 410P9M and 403U7N weremeasured using a Beckman Coulter LS Particle Size Analyzer. Compositions410P9M and 403U7N are characterized in the table below:

TABLE 410P9M and 403U7N Characterization 410P9M 403U7N Acetochlorloading 33.0%   41% Shell Wall Amount  8% 7.1%  (% organic premix) Amineexcess 20%  5% Acetochlor/NORPAR 18.5 8.4 Mean Particle size 10 μm 12-13μm

Example 3. Study of Soybean, Cotton, Rice, Peanut and Wheat Safety inPreemergent Crop Application of Microencapsulated AcetochlorFormulations

Aqueous dispersions of the two microencapsulated acetochlorformulations, referenced as 410P9M and 403U7N, prepared in Example 2were applied to soil immediately after seeding with glyphosate-tolerant(ROUNDUP READY) soybean, glyphosate-tolerant (ROUNDUP READY) cotton,rice, peanut or wheat. Formulations were tested against commercialformulations HARNESS and DEGREE. Formulations were applied preemergentto soybean, cotton, rice, peanut and wheat and measured forphytotoxicity at 19, 20, 21, 22, or 25 DAT. The results are shown intables below (Soybean % Injury 22 DAT), (Soybean % Injury 22 DAT),(Soybean % Injury 20 DAT), (Cotton % Injury 20 DAT), (Rice % Injury 25DAT), (Peanut % Injury 25 DAT), (Winter Wheat % Injury 21 DAT).

Pots were seeded with RR2Y soybeans and then immediately treated withHARNESS, DEGREE or an aqueous dispersion of 410P9M or 403U7N withapplication rates of 420, 700, 980, 1260 or 1543 g/ha (0.375, 0.625,0.875, 1.125 or 1.375 lb/A). Plants were watered by overhead irrigation(0.25″ or 6.4 mm) 3 days after herbicide treatment followed bysub-irrigation to start germination. After germination pots weresub-irrigated as needed. Plants were evaluated 22 DAT for foliar injuryand the results are reported in the table below.

TABLE Soybean % Injury 22 DAT Soybean Product Rate GLXMG TRT Formulation% AI g/ha AI (Avg. 6 reps) 1 HARNESS 74.8 420 2.0 2 HARNESS 74.8 700 4.23 HARNESS 74.8 980 11.2 4 HARNESS 74.8 1260 22.0 5 HARNESS 74.8 154024.2 6 DEGREE 42.0 420 0.5 7 DEGREE 42.0 700 3.3 8 DEGREE 42.0 980 2.7 9DEGREE 42.0 1260 4.7 10 DEGREE 42.0 1540 6.3 11 403U7N 41.0 420 0.7 12403U7N 41.0 700 1.3 13 403U7N 41.0 980 2.0 14 403U7N 41.0 1260 2.7 15403U7N 41.0 1540 3.8 16 410P9M 33.0 420 0.3 17 410P9M 33.0 700 0.8 18410P9M 33.0 980 0.8 19 410P9M 33.0 1260 1.3 20 410P9M 33.0 1540 3.0 21Untreated 0 0.0

Pots were seeded with RR2Y soybeans and then immediately treated withHARNESS, DEGREE or an aqueous dispersion of 410P9M, 403U7N or a 50:50blend of 410P9M:403U7N with application rates of 420, 700, 980, 1260 or1540 g/ha (0.375, 0.625, 0.875, 1.125, or 1.375 lb/A). Plants wereevaluated 22 DAT for injury and the results are reported in the tablebelow.

TABLE Soybean % Injury 22 DAT Soybean Product Rate GLXMG TRT Formulation% AI g/ha AI (Avg. 6 reps) 1 HARNESS 74.8 420 4.0 2 HARNESS 74.8 700 6.23 HARNESS 74.8 980 9.0 4 HARNESS 74.8 1260 12.3 5 HARNESS 74.8 1540 30.06 DEGREE 42.0 420 1.7 7 DEGREE 42.0 700 3.7 8 DEGREE 42.0 980 5.0 9DEGREE 42.0 1260 17.3 10 DEGREE 42.0 1540 5.0 11 403U7N 41.0 420 2.3 12403U7N 41.0 700 3.7 13 403U7N 41.0 980 8.0 14 403U7N 41.0 1260 2.3 15403U7N 41.0 1540 4.0 16 410P9M 33.0 420 2.0 17 410P9M 33.0 700 1.7 18410P9M 33.0 980 3.3 19 410P9M 33.0 1260 2.0 20 410P9M 33.0 1540 7.0 21403U7N 41.0 210 2.0 410P9M 33.0 210 22 403U7N 41.0 350 1.7 410P9M 33.0350 23 403U7N 41.0 490 3.3 410P9M 33.0 490 24 403U7N 41.0 630 1.7 410P9M33.0 630 25 403U7N 41.0 770 4.3 410P9M 33.0 770 26 Untreated — 0 0.0

Soybean injury was greatest with HARNESS compared to any of theencapsulated acetochlor treatments used.

Pots were seeded with RR2Y soybean then immediately treated withHARNESS, DEGREE or an aqueous dispersion of 410P9M, 403U7N or a 50:50blend of 410P9M:403U7N with application rates of 560, 1120, 2240 or 4485g/ha (0.5, 1.0, 2.0, or 4.0 lb/A). Plants were evaluated 20 DAT forfoliar injury and the results are reported in the table below.

TABLE Soybean % Injury 20 DAT Soybean Product Rate GLXMG TRT Formulation% AI g/ha AI (Avg. 6 reps) 1 HARNESS 74.8 560 6.3 2 HARNESS 74.8 11206.8 3 HARNESS 74.8 2240 12.0 4 HARNESS 74.8 4485 28.3 5 DEGREE 42.0 5604.0 6 DEGREE 42.0 1120 3.7 7 DEGREE 42.0 2240 5.3 8 DEGREE 42.0 448517.5 9 403U7N 41.0 560 4.7 10 403U7N 41.0 1120 3.0 11 403U7N 41.0 22404.3 12 403U7N 41.0 4485 5.3 13 410P9M 33.0 560 2.7 14 410P9M 33.0 11204.7 15 410P9M 33.0 2240 4.3 16 410P9M 33.0 4485 5.3 17 403U7N 41.0 2801.3 410P9M 33.0 280 18 403U7N 41.0 560 3.3 410P9M 33.0 560 19 403U7N41.0 1120 3.0 410P9M 33.0 1120 20 403U7N 41.0 2242 4.7 410P9M 33.0 224321 Untreated 0 0.0

In this study, HARNESS caused more soybean injury than any of theencapsulated acetochlor formulations tested. At the two highest ratestested, the formulations containing encapsulated acetochlor compositions410P9M and 403U7N caused less injury to soybeans than DEGREE.

Pots were seeded with ROUNDUP READY Flex Cotton and then immediatelytreated with HARNESS, DEGREE or an aqueous dispersion of 410P9M, 403U7Nor a 50:50 blend of 410P9M:403U7N with application rates of 560, 1120,2240 or 4485 g/ha (0.5, 1.0, 2.0, or 4.0 lb/A). Plants were evaluated 20DAT for foliar injury and the results are reported in the table below.

TABLE Cotton % Injury 20 DAT Cotton Product Rate GOSHI TRT Formulation %AI g/ha AI (Avg. 6 reps) 1 HARNESS 74.8 560 2.7 2 HARNESS 74.8 1120 3.33 HARNESS 74.8 2240 8.0 4 HARNESS 74.8 4485 35.8 5 DEGREE 42.0 560 2.3 6DEGREE 42.0 1120 2.0 7 DEGREE 42.0 2240 3.7 8 DEGREE 42.0 4485 4.7 9403U7N 41.0 560 0.2 10 403U7N 41.0 1120 1.2 11 403U7N 41.0 2240 6.6 12403U7N 41.0 4485 6.7 13 410P9M 33.0 560 0.8 14 410P9M 33.0 1120 1.3 15410P9M 33.0 2240 3.7 16 410P9M 33.0 4485 3.3 17 403U7N 41.0 280 0.7410P9M 33.0 280 18 403U7N 41.0 560 3.0 410P9M 33.0 560 19 403U7N 41.01120 4.6 410P9M 33.0 1120 20 403U7N 41.0 2242 4.8 410P9M 33.0 2243 21Untreated 0 0.0

In this study, the encapsulated acetochlor formulations caused lessinjury to cotton than HARNESS.

Pots were seeded with rice and then immediately treated with HARNESS,DEGREE or an aqueous dispersion of 410P9M, 403U7N or a 50:50 blend of410P9M:403U7N with application rates of 560, 1120, 2240 or 4485 g/ha(0.5, 1.0, 2.0, or 4.0 lb/A). Plants were evaluated 25 DAT for foliarinjury and the results are reported in the table below.

TABLE Rice % Injury 25 DAT Rice Product Rate ORYSS TRT Formulation % AIg/ha AI (Avg. 5 reps) 1 HARNESS 74.8 560 4.3 2 HARNESS 74.8 1120 12.5 3HARNESS 74.8 2240 19.2 4 HARNESS 74.8 4485 79.2 5 DEGREE 42.0 560 4.3 6DEGREE 42.0 1120 6.7 7 DEGREE 42.0 2240 15.0 8 DEGREE 42.0 4485 22.5 9403U7N 41.0 560 3.3 10 403U7N 41.0 1120 5.7 11 403U7N 41.0 2240 10.0 12403U7N 41.0 4485 13.3 13 410P9M 33.0 560 2.7 14 410P9M 33.0 1120 6.0 15410P9M 33.0 2240 8.7 16 410P9M 33.0 4485 14.2 17 403U7N 41.0 280 6.8410P9M 33.0 280 18 403U7N 41.0 560 9.2 410P9M 33.0 560 19 403U7N 41.01120 10.8 4 10P9M 33.0 1120 20 403U7N 41.0 2242 24.2 410P9M 33.0 2243 21Untreated 0 0.0

In this study, rice foliar injury was greater with HARNESS compared toany of the encapsulated acetochlor formulations.

Pots were seeded with peanuts and then immediately treated with HARNESS,DEGREE or an aqueous dispersion of 410P9M, 403U7N or a 50:50 blend of410P9M:403U7N with application rates of 560, 1120, 2240 or 4485 g/ha(0.5, 1.0, 2.0, or 4.0 lb/A). Plants were evaluated 25 DAT for foliarinjury and the results are reported in the table below.

TABLE Peanut % Injury 25 DAT Peanut Product Rate ARHHY TRT Formulation %AI g/ha AI (Avg. 5 reps) 1 HARNESS 74.8 560 7.5 2 HARNESS 74.8 1120 7.03 HARNESS 74.8 2240 12.5 4 HARNESS 74.8 4485 18.3 5 DEGREE 42.0 560 4.06 DEGREE 42.0 1120 4.8 7 DEGREE 42.0 2240 6.5 8 DEGREE 42.0 4485 7.3 9403U7N 41.0 560 2.3 10 403U7N 41.0 1120 2.0 11 403U7N 41.0 2240 4.7 12403U7N 41.0 4485 4.8 13 410P9M 33.0 560 3.7 14 410P9M 33.0 1120 4.7 15410P9M 33.0 2240 3.7 16 410P9M 33.0 4485 7.0 17 403U7N 41.0 280 2.0410P9M 33.0 280 18 403U7N 41.0 560 5.5 410P9M 33.0 560 19 403U7N 41.01120 6.4 410P9M 33.0 1120 20 403U7N 41.0 2242 8.2 410P9M 33.0 2243 21Untreated 0 0.0

The encapsulated acetochlor formulations showed greater crop safety inpeanut than HARNESS.

Pots containing a 50:50 silt loam:redi-earth soil mix were seeded withwinter wheat. Immediately after planting, preemergence applications ofHARNESS, DEGREE or an aqueous dispersion of 410P9M or 403U7N atapplication rates of 420, 841, 1261, and 1681 g/ha were conducted.Plants were evaluated 21 DAT for foliar injury and the results arereported in the table below.

TABLE Winter Wheat % Injury 21 DAT Wheat Product Rate TRZAW TRTFormulation g/l AI g/ha AI (Avg 6 reps) 1 410P9M 359 420 0.0 2 410P9M359 841 3.3 3 410P9M 359 1261 3.3 4 410P9M 359 1681 2.5 5 403U7N 455 4200.8 6 403U7N 455 841 2.5 7 403U7N 455 1261 2.5 8 403U7N 455 1681 3.3 9DEGREE 455 420 2.5 10 DEGREE 455 841 2.5 11 DEGREE 455 1261 5.0 12DEGREE 455 1681 6.7 13 HARNESS 839 420 7.5 14 HARNESS 839 841 10.8 15HARNESS 839 1261 10.0 16 HARNESS 839 1681 19.2 17 Untreated 0 0.0

The encapsulated acetochlor formulations showed greater crop safety inwheat than HARNESS.

Example 4. Study of Weed Control Efficacy and Soybean and Cotton Safetyin Preemergent Crop Application of Microencapsulated AcetochlorFormulations and Tank Mixes with Other Herbicides

Formulations and mixtures were applied to soil immediately after seedingwith herbicide-tolerant soybean (glyphosate-tolerant, ROUNDUP READY soyor dicamba-tolerant, DT-SOY) or herbicide-tolerant cotton(glyphosate-tolerant, ROUNDUP READY cotton or dicamba-tolerant,DT-COTTON) to assess crop safety and Proso Millet (PANMI), Velvetleaf(ABUTH), Purslane (POROL), Morningglory (IPOLA), or Rox Orange Sorghum(SORSS) to assess weed efficacy.

Aqueous dispersions of microencapsulated acetochlor formulation 410P9Mprepared in Example 2, alone and in tank mix combination with VALOR SX(flumioxazin), REFLEX (fomesafen), SHARPEN (saflufenacil), or CLARITY(dicamba, diglycolamine salt) were tested. Formulations and mixtureswere tested against commercial formulation HARNESS. All treatments wereapplied immediately to seeded soil and allowed to sit for 3 days (toobtain release of acetochlor in formulations of 410P9M) in thegreenhouse prior to receiving 0.25 or 0.5 inches (6.4 or 13 mm) ofoverhead irrigation to incorporate the herbicide treatments into thesoil surface and evaluated 14, 16, or 17 DAT. The results are shown inthe first Table below (Soybean and Cotton % Injury 16 DAT and IPOLA andSORSS Weed Control Efficacy 16 DAT) and the second Table below (Soybeanand Cotton % Injury 17 DAT and PANMI, ABUTH, POROL Weed Control Efficacy14 DAT).

TABLE Soybean and Cotton % Injury 16 DAT and IPOLA and SORSS WeedControl Efficacy 16 DAT Product RR RR Cotton TRT Formulation % AI Rateg/ha Soy GLXMV GOSHX IPOLA SORSS 1 410P9M 33.0 1120 8.3 2.5 0.8 5.8 2410P9M 33.0 1682 10.8 5.8 3.3 30.0 3 410P9M 33.0 2244 17.5 16.7 30.845.8 4 HARNESS 74.8 1120 33.3 22.5 18.3 48.3 5 HARNESS 74.8 1682 63.335.0 41.7 65.8 6 HARNESS 74.8 2244 84.2 46.7 78.3 82.5 7 VALOR SX 50.035 0.0 0.0 12.5 30.8 8 VALOR SX 50.0 70 5.8 22.5 21.7 35.8 9 VALOR SX50.0 140 17.5 20.0 55.0 60.0 10 REFLEX 22.8 95 0.0 0.0 1.7 15.8 11REFLEX 22.8 190 4.2 15.8 61.7 30.0 12 REFLEX 22.8 380 6.7 12.5 81.7 79.213 SHARPEN 34.2 25 0.0 0.0 56.7 3.3 14 SHARPEN 34.2 50 1.7 7.5 100.027.5 15 SHARPEN 34.2 100 21.7 12.5 100.0 32.5 16 410P9M 33.0 1120 5.00.0 2.5 20.8 VALOR SX 50.0 35 17 410P9M 33.0 1682 7.5 8.3 5.8 35.0 VALORSX 50.0 35 18 410P9M 33.0 2244 20.8 9.2 33.3 53.3 VALOR SX 50.0 35 19410P9M 33.0 1120 6.7 0.0 17.5 31.7 VALOR SX 50.0 70 20 410P9M 33.0 16823.3 5.8 30.8 49.2 VALOR SX 50.0 70 21 410P9M 33.0 2244 24.2 10.0 46.770.0 VALOR SX 50.0 70 22 410P9M 33.0 1120 10.0 0.0 35.8 51.7 VALOR SX50.0 140 23 410P9M 33.0 1682 9.2 10.0 43.3 59.2 VALOR SX 50.0 140 24410P9M 33.0 2244 43.3 9.2 61.7 71.7 VALOR SX 50.0 140 25 410P9M 33.01120 0.0 3.3 7.5 20.0 REFLEX 50.0 95 26 410P9M 33.0 1682 4.2 5.8 29.234.2 REFLEX 50.0 95 27 410P9M 33.0 2244 14.2 10.8 45.0 38.3 REFLEX 50.095 28 410P9M 33.0 1120 0.8 5.0 15.8 38.3 REFLEX 50.0 190 29 410P9M 33.01682 1.7 10.0 60.0 37.5 REFLEX 50.0 190 30 410P9M 33.0 2244 21.7 12.555.0 47.5 REFLEX 50.0 190 31 410P9M 33.0 1120 4.2 0.0 53.3 81.7 REFLEX50.0 380 32 410P9M 33.0 1682 5.0 10.0 64.2 74.2 REFLEX 50.0 380 33410P9M 33.0 2244 7.5 18.3 76.7 76.7 REFLEX 50.0 380 34 410P9M 33.0 11205.8 1.7 25.8 25.0 SHARPEN 34.2 25 35 410P9M 33.0 1682 5.8 14.2 86.7 30.0SHARPEN 34.2 25 36 410P9M 33.0 2244 10.0 16.7 89.2 33.3 SHARPEN 34.2 2537 410P9M 33.0 1120 6.7 7.5 93.3 45.0 SHARPEN 34.2 50 38 410P9M 33.01682 15.0 5.0 100.0 55.8 SHARPEN 34.2 50 39 410P9M 33.0 2244 15.8 26.793.3 51.7 SHARPEN 34.2 50 40 410P9M 33.0 1120 5.0 9.2 100.0 40.8 SHARPEN34.2 100 41 410P9M 33.0 1682 10.0 11.7 85.0 49.2 SHARPEN 34.2 100 42410P9M 33.0 2244 19.2 13.3 98.3 54.2 SHARPEN 34.2 100 43 Untreated 0 00.0 0.0 0.0 0.0

Encapsulated acetochlor formulation 410P9M showed acceptable levels ofcrop safety at the 1120 g/ha rate, both alone and in combination withcommercial herbicides VALOR SX, REFLEX and SHARPEN. Encapsulatedacetochlor formulation 410P9M showed acceptable levels of crop safety atthe 1682 g/ha rate with commercial herbicide VALOR SX and REFLEX.

TABLE Soybean and Cotton % Injury 17 DAT and PANMI, ABUTH, POROL WeedControl Efficacy 14 DAT DT- Product Rate DT-SOY COTTON TRT Formulation %AI g/ha GLXMD GOSHD PANMI ABUTH POROL 1 HARNESS 74.8 840 6.7 1.7 98.37.5 99.5 2 1260 29.2 12.5 99.3 25.8 100.0 3 410P9M 33.0 840 0.0 0.0 76.50.0 35.0 4 1260 9.2 0.8 88.0 19.2 64.2 5 VALOR SX 50.0 35 0.8 0.0 50.831.7 99.7 6 70 6.7 15.0 66.7 63.3 100.0 7 REFLEX 22.8 95 4.2 2.5 20.021.7 81.7 8 190 5.0 10.0 40.8 48.3 96.8 9 SHARPEN 34.2 25 2.5 4.2 39.246.7 99.7 10 50 6.7 12.5 56.7 87.5 100.0 11 CLARITY 38.5 140 0.0 0.016.7 28.3 58.3 12 280 0.0 0.0 41.7 46.7 77.5 13 410P9M 33.0 840 1.7 0.052.5 14.2 83.3 VALOR SX 50.0 35 14 410P9M 33.0 1260 10.0 4.2 70.0 38.393.3 VALOR SX 50.0 35 15 410P9M 33.0 840 7.5 7.5 62.5 11.7 88.8 VALOR SX50.0 70 16 410P9M 33.0 1260 23.3 8.3 73.0 46.7 93.3 VALOR SX 50.0 70 17410P9M 33.0 840 0.8 4.2 31.7 2.5 63.3 REFLEX 50.0 95 18 410P9M 33.0 126012.5 6.7 58.3 27.5 72.5 REFELX 50.0 95 19 410P9M 33.0 840 10.8 7.5 75.015.8 85.0 REFLEX 50.0 190 20 410P9M 33.0 1260 15.8 10.8 83.0 29.2 91.3REFELX 50.0 190 21 410P9M 33.0 840 8.3 5.8 62.5 30.0 88.0 SHARPEN 34.225 22 410P9M 33.0 1260 10.0 9.2 77.5 50.0 99.3 SHARPEN 34.2 25 23 410P9M33.0 840 15.0 7.5 65.8 92.5 99.7 SHARPEN 34.2 50 24 410P9M 33.0 126017.5 25.8 82.2 97.5 100.0 SHARPEN 34.2 50 25 410P9M 33.0 840 0.0 0.065.8 25.8 60.8 CLARITY 38.5 140 26 410P9M 33.0 1260 11.7 4.2 82.5 33.371.7 CLARITY 38.5 140 27 410P9M 33.0 840 0.0 0.0 65.0 30.0 79.2 CLARITY38.5 280 28 410P9M 33.0 1260 12.5 5.0 82.0 45.0 89.3 CLARITY 38.5 280 29Untreated 0.0 0 0.0 0.0 0.0 0.0 0.0

Tank mixtures of encapsulated acetochlor formulation 410P9M with SHARPENprovided the best weed control compared to other tank mixtures tested.

Pots containing a 50:50 silt loam:redi-earth soil mix were seeded withwinter wheat. Immediately after planting, encapsulated acetochlorformulation 410P9M at 840, 1260, and 1680 g ai/ha and SENCOR DF(metribuzin) at 210, 420, and 840 g ai/ha were applied. In addition,encapsulated acetochlor formulation 410P9M was tank-mixed with SENCOR DF(metribuzin) at each rate. Then, the herbicide treatments wereincorporated into the germination zone with 0.25 inches (6.4 mm)overhead irrigation three days after application.

After the incorporation of the herbicide treatments, the pots were onlyoverhead irrigated as needed to ensure proper incorporation of theherbicides in the germination zone.

The plants were rated visually and percentage of crop injury wasdetermined 19 days after the herbicide treatments. The results arereported in the table below.

TABLE Winter Wheat % Injury 19 DAT Product Rate Wheat TRT Formulationg/l AI % AI g/ha AI TRZAW 1 410P9M 359 840 1.7 2 410P9M 359 1260 1.7 3410P9M 359 1680 1.7 4 SENCOR DF 75 210 90.8 5 SENCOR DF 75 420 100.0 6SENCOR DF 75 840 100.0 7 410P9M 359 840 100.0 SENCOR DF 75 210 8 410P9M359 840 91.7 SENCOR DF 75 420 9 410P9M 359 840 100.0 SENCOR DF 75 840 10410P9M 359 1260 95.8 SENCOR DF 75 210 11 410P9M 359 1260 97.5 SENCOR DF75 420 12 410P9M 359 1260 100.0 SENCOR DF 75 840 13 410P9M 359 1680100.0 SENCOR DF 75 210 14 410P9M 359 1680 100.0 SENCOR DF 75 420 15410P9M 359 1680 100.0 SENCOR DF 75 840 16 Untreated 0 0 0.0

Example 5. Field Trial Study of Weed Control Efficacy and Soybean andCotton Safety in Preemergent Crop Application of MicroencapsulatedAcetochlor Formulations and Tank Mixtures with Other Herbicides

Aqueous dispersions of microencapsulated acetochlor formulation 410P9Mprepared in Example 2, alone and in tank mix combination with VALOR SX(flumioxazin), COTORAN 4 (fluometuron) and SENCOR DF (metribuzin) weretested. The commercial formulation DUAL MAGNUM, available from Syngentaand comprising s-metalochlor as the active ingredient and proprietaryingredients was also tested. All treatments were applied to soil seededwith glyphosate-tolerant ROUNDUP READY soybeans or ROUNDUP READY FlexCotton on the same day as planting and the associated crop injury wasevaluated. Crop injury was evaluated in terms of growth reduction (%GR), stand reduction (% SR) and leaf crinkle (% LF). The results fromthree field trials are reported in the tables below.

TABLE RR Soybean % Crop Injury 14 DAT in Three Field Trials Rate TrialTrial Trial Product g 2010530037 2010530038 2010530039 Formulation AI/ha% GR % LF % GR % LF % GR % LF 410P9M 840 0.0 0.0 0.8 3.3 6.3 10.0 410P9M1260 0.0 2.0 1.3 5.8 6.3 11.3 DUAL 930 0.0 0.0 0.0 0.8 5.0 8.8 MAGNUMDUAL 1400 0.0 1.6 0.0 0.0 5.0 11.3 MAGNUM COTORAN 4 1120 0.0 0.8 0.0 0.07.5 1.3 COTORAN 4 1800 0.0 1.5 0.0 0.8 32.5 0.0 VALOR SX 48 0.0 0.8 0.80.0 25.0 7.5 VALOR SX 70 0.0 2.8 0.0 0.0 30.0 7.5 SENCOR DF 370 0.0 0.00.0 0.0 66.3 0.0 SENCOR DF 560 0.0 0.0 3.8 0.0 73.8 . 410P9M 840 0.0 4.01.3 9.5 36.3 18.8 VALOR SX 48 410P9M 1260 0.0 5.8 1.3 11.3 32.5 15.0VALOR SX 48 410P9M 840 0.0 5.8 3.3 9.3 48.8 15.0 VALOR SX 70 410P9M 12600.0 9.0 4.5 13.8 51.3 17.5 VALOR SX 70 410P9M 840 0.0 0.0 2.8 7.5 22.515.0 COTORAN 4 1120 410P9M 1260 0.0 0.8 2.0 10.0 21.3 12.5 COTORAN 41120 410P9M 840 0.0 2.0 7.0 8.3 32.5 15.0 COTORAN 4 1800 410P9M 1260 0.03.3 5.8 11.3 42.5 15.0 COTORAN 4 1800 410P9M 840 0.0 2.0 3.8 9.3 70.011.3 SENCOR DF 370 410P9M 1260 0.0 4.0 2.0 8.3 85.0 7.5 SENCOR DF 370410P9M 840 0.0 0.8 11.3 7.5 90.0 15.0 SENCOR DF 560 410P9M 1260 0.0 3.512.5 9.5 100.0 — SENCOR DF 560

Data from these field trials demonstrate that the encapsulatedacetochlor formulation 410P9M exhibited good soybean crop safety aloneat all three locations tested and exhibited good soybean crop safety incombination with co-herbicides VALOR SX, COTORAN 4 and SENCOR DF at twoof the three locations tested.

TABLE RR Flex Cotton % Crop Injury 14 DAT in Three Field Trials RateTrial Trial Trial Product g 2010530037 2010530038 2010530039 FormulationAI/ha % GR % SR % GR % SR % GR % SR 410P9M 840 0.0 0.0 2.5 0.0 2.5 0.0410P9M 1260 0.0 0.0 0.0 0.0 6.3 0.0 DUAL 930 1.3 0.0 3.8 0.0 3.8 0.0MAGNUM DUAL 1400 6.5 0.0 7.8 0.0 20.0 3.8 MAGNUM COTORAN 4 1120 0.0 0.00.8 0.0 2.5 0.0 COTORAN 4 1800 2.5 2.5 0.8 0.0 1.3 0.0 VALOR SX 48 22.525.0 12.0 7.0 47.5 11.3 VALOR SX 70 38.8 41.3 37.5 28.8 65.0 30.0 SENCORDF 370 99.3 99.3 86.3 86.3 92.5 92.5 SENCOR DF 560 99.5 99.5 100.0 100.098.8 98.8 410P9M 840 6.3 3.8 46.3 33.8 71.3 55.0 VALOR SX 48 410P9M 12606.3 0.0 56.3 56.3 60.0 32.5 VALOR SX 48 410P9M 840 12.5 11.3 66.3 66.380.0 66.3 VALOR SX 70 410P9M 1260 21.3 15.0 65.0 57.5 83.8 75.0 VALOR SX70 410P9M 840 0.0 0.0 1.3 0.0 8.8 1.3 COTORAN 4 1120 410P9M 1260 0.0 0.00.0 0.0 22.5 7.5 COTORAN 4 1120 410P9M 840 1.3 1.3 0.0 0.0 11.3 5.0COTORAN 4 1800 410P9M 1260 1.3 1.3 0.0 0.0 22.5 5.0 COTORAN 4 1800410P9M 840 87.3 87.3 62.5 68.8 100.0 100.0 SENCOR DF 370 410P9M 126091.3 90.0 68.3 70.8 100.0 100.0 SENCOR DF 370 410P9M 840 98.5 98.5 95.895.8 100.0 100.0 SENCOR DF 560 410P9M 1260 92.5 87.5 97.5 97.5 100.0100.0 SENCOR DF 560

Data from these field trials demonstrate that the encapsulatedacetochlor formulation 410P9M both alone and in combination with COTORAN4 has good crop safety on cotton. Tank mixes of formulation 410P9M withVALOR SX and SENCOR DF did not exhibit acceptable levels of crop safety.This is not unexpected since SENCOR DF is not labeled for use in cottonand VALOR SX requires a 14-28 day waiting period after application priorto planting cotton.

The efficacy of the same formulations on morningglory (IPOHE),amaranthus (AMASS) and sicklepod (CASOB) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE IPOHE, AMASS and CASOB Weed Control Efficacy 28 and 56 DAT ProductRate g IPOHE IPOHE AMASS AMASS CASOB CASOB Formulation AI/ha 28 DAT 56DAT 28 DAT 56 DAT 28 DAT 56 DAT 410P9M 840 0.0 6.3 55.0 42.5 5.0 0.0410P9M 1260 8.8 6.3 85.0 72.5 21.3 28.8 DUAL 930 0.0 0.0 77.5 47.5 25.05.0 MAGNUM DUAL 1400 3.8 0.0 80.0 50.0 32.5 10.0 MAGNUM COTORAN 4 11200.0 12.5 0.0 0.0 17.5 0.0 COTORAN 4 1800 10.0 0.0 10.0 10.0 36.3 0.0VALOR SX 48 73.8 40.0 100.0 85.0 60.0 27.5 VALOR SX 70 73.8 72.5 100.075.0 50.0 7.5 SENCOR DF 370 10.0 0.0 92.5 60.0 75.0 60.0 SENCOR DF 5607.5 0.0 100.0 65.0 97.0 100.0 410P9M 840 66.3 60.0 100.0 87.5 55.0 42.5VALOR SX 48 410P9M 1260 48.8 31.3 100.0 100.0 56.3 26.3 VALOR SX 48410P9M 840 92.5 82.5 100.0 100.0 80.0 70.0 VALOR SX 70 410P9M 1260 65.052.5 100.0 100.0 75.8 37.5 VALOR SX 70 410P9M 840 3.8 0.0 100.0 100.056.3 32.5 COTORAN 4 1120 410P9M 1260 7.5 0.0 100.0 85.0 35.0 25.0COTORAN 4 1120 410P9M 840 16.3 10.0 100.0 100.0 38.8 5.0 COTORAN 4 1800410P9M 1260 7.5 6.3 100.0 100.0 36.3 0.0 COTORAN 4 1800 410P9M 840 3.80.0 100.0 96.3 80.0 60.0 SENCOR DF 370 410P9M 1260 3.8 0.0 100.0 100.067.5 36.3 SENCOR DF 370 410P9M 840 0.0 0.0 100.0 100.0 94.5 67.5 SENCORDF 560 410P9M 1260 16.3 0.0 100.0 100.0 100.0 80.0 SENCOR DF 560

The efficacy of the same formulations on velvetleaf (ABUTH),barnyardgrass (ECHCG) and signalgrass (BRAPP) by preemergent applicationon the same day as planting the crop was also determined with theresults reported in the table below.

TABLE ABUTH, ECHCG and BRAPP Weed Control Efficacy 28 and 56 DAT ProductRate ABUTH ABUTH ECHCG ECHCG BRAPP BRAPP Formulation g AI/ha 28 DAT 56DAT 28 DAT 56 DAT 28 DAT 56 DAT 410P9M 840 0.0 0.0 80.0 50.0 10.0 0.0410P9M 1260 3.8 0.0 100.0 100.0 35.0 0.0 DUAL MAGNUM 930 11.3 0.0 100.0100.0 75.0 27.5 DUAL MAGNUM 1400 32.5 15.0 92.5 100.0 85.0 15.0 COTORAN4 1120 0.0 0.0 25.0 0.0 0.0 0.0 COTORAN 4 1800 3.8 0.0 60.0 0.0 32.5 0.0VALOR SX 48 100.0 82.5 75.0 20.0 20.0 5.0 VALOR SX 70 100.0 100.0 75.072.5 25.0 20.0 SENCOR DF 370 100.0 90.0 97.5 27.5 25.0 10.0 SENCOR DF560 100.0 100.0 90.0 75.0 45.0 10.0 410P9M 840 89.5 82.5 99.8 87.5 58.822.5 VALOR SX 48 410P9M 1260 90.0 85.0 100.0 100.0 26.3 5.0 VALOR SX 48410P9M 840 100.0 100.0 97.5 100.0 45.0 35.0 VALOR SX 70 410P9M 1260 91.380.0 100.0 100.0 40.0 0.0 VALOR SX 70 410P9M 840 0.0 0.0 100.0 100.047.5 12.5 COTORAN 4 1120 410P9M 1260 3.8 0.0 85.0 100.0 28.8 0.0 COTORAN4 1120 410P9M 840 10.0 5.0 95.0 100.0 82.5 35.0 COTORAN 4 1800 410P9M1260 3.8 0.0 100.0 100.0 40.0 5.0 COTORAN 4 1800 410P9M 840 95.0 85.0100.0 100.0 75.0 17.5 SENCOR DF 370 410P9M 1260 100.0 97.5 100.0 100.072.5 25.0 SENCOR DF 370 410P9M 840 100.0 100.0 100.0 100.0 87.5 46.3SENCOR DF 560 410P9M 1260 95.0 97.5 100.0 100.0 97.5 47.5 SENCOR DF 560

The efficacy of the same formulations on amaranthus (AMASS), velvetleaf(ABUTH) and morningglory (IPOHE) by preemergent application on the sameday as planting the crop was also determined with the results reportedin the table below.

TABLE AMASS, ABUTH and IPOHE Weed Control Efficacy 28 DAT Product RateAMASS ABUTH IPOHE Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 840100.0 16.3 17.5 410P9M 1260 100.0 23.8 17.5 DUAL MAGNUM 930 100.0 22.516.3 DUAL MAGNUM 1400 100.0 18.8 21.3 COTORAN 4 1120 95.0 16.3 18.8COTORAN 4 1800 92.5 28.8 21.3 VALOR SX 48 100.0 94.5 58.8 VALOR SX 70100.0 99.8 88.8 SENCOR DF 370 100.0 80.0 16.3 SENCOR DF 560 100.0 97.518.8 410P9M 840 100.0 93.8 81.3 VALOR SX 48 410P9M 1260 100.0 97.0 89.5VALOR SX 48 410P9M 840 100.0 100.0 85.0 VALOR SX 70 410P9M 1260 100.0100.0 78.8 VALOR SX 70 410P9M 840 100.0 22.5 22.5 COTORAN 4 1120 410P9M1260 100.0 66.3 28.8 COTORAN 4 1120 410P9M 840 100.0 36.3 41.3 COTORAN 41800 410P9M 1260 100.0 41.3 25.0 COTORAN 4 1800 410P9M 840 62.5 100.025.0 SENCOR DF 370 410P9M 1260 68.3 94.5 20.0 SENCOR DF 370 410P9M 84095.8 100.0 28.8 SENCOR DF 560 410P9M 1260 97.5 99.8 21.3 SENCOR DF 560

The efficacy of the same formulations on sicklepod (CASOB), hempsesbania (SEBEX) and signalgrass (BRAPP) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE CASOB, SEBEX and BRAPP Weed Control Efficacy 28 DAT Product RateCASOB SEBEX BRAPP Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84022.5 8.8 60.0 410P9M 1260 16.3 18.8 66.3 DUAL MAGNUM 930 10.0 3.8 90.0DUAL MAGNUM 1400 21.3 23.8 92.5 COTORAN 4 1120 25.0 13.8 5.0 COTORAN 41800 30.0 41.3 48.8 VALOR SX 48 47.5 78.3 15.0 VALOR SX 70 58.8 81.327.5 SENCOR DF 370 56.3 54.5 40.0 SENCOR DF 560 74.5 78.3 58.8 410P9M840 63.8 85.8 86.3 VALOR SX 48 410P9M 1260 62.5 90.0 85.0 VALOR SX 48410P9M 840 66.3 88.8 66.3 VALOR SX 70 410P9M 1260 72.5 95.8 83.8 VALORSX 70 410P9M 840 21.3 36.3 88.8 COTORAN 4 1120 410P9M 1260 23.8 51.360.8 COTORAN 4 1120 410P9M 840 42.5 71.3 93.8 COTORAN 4 1800 410P9M 126045.0 83.3 100.0 COTORAN 4 1800 410P9M 840 56.3 73.8 93.8 SENCOR DF 370410P9M 1260 56.3 66.3 97.5 SENCOR DF 370 410P9M 840 72.0 91.3 96.3SENCOR DF 560 410P9M 1260 80.8 100.0 100.0 SENCOR DF 560

The efficacy of the same formulations on crowfootgrass (DTTAE),barnyardgrass (ECHCG) and goosegrass (ELEIN) by preemergent applicationon the same day as planting the crop was also determined with theresults reported in the table below.

TABLE DTTAE, ECHCG and ELEIN Weed Control Efficacy 28 DAT Product RateDTTAE ECHCG ELEIN Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84093.8 97.5 100.0 410P9M 1260 100.0 100.0 100.0 DUAL MAGNUM 930 100.0100.0 100.0 DUAL MAGNUM 1400 92.5 100.0 100.0 COTORAN 4 1120 57.5 97.5100.0 COTORAN 4 1800 87.5 83.8 100.0 VALOR SX 48 95.0 86.3 100.0 VALORSX 70 90.0 95.0 92.5 SENCOR DF 370 92.5 90.0 100.0 SENCOR DF 560 93.8100.0 100.0 410P9M 840 100.0 100.0 100.0 VALOR SX 48 410P9M 1260 100.0100.0 100.0 VALOR SX 48 410P9M 840 100.0 100.0 100.0 VALOR SX 70 410P9M1260 100.0 100.0 100.0 VALOR SX 70 410P9M 840 100.0 97.5 100.0 COTORAN 41120 410P9M 1260 90.0 100.0 100.0 COTORAN 4 1120 410P9M 840 92.5 100.0100.0 COTORAN 4 1800 410P9M 1260 100.0 100.0 100.0 COTORAN 4 1800 410P9M840 100.0 100.0 100.0 SENCOR DF 370 410P9M 1260 100.0 100.0 100.0 SENCORDF 370 410P9M 840 100.0 100.0 100.0 SENCOR DF 560 410P9M 1260 100.0100.0 100.0 SENCOR DF 560

The efficacy of the same formulations on amaranth (AMARE), velvetleaf(ABUTH) and crabgrass (DIGSA) by preemergent application on the same dayas planting the crop was also determined with the results reported inthe table below.

TABLE AMARE, ABUTH and DIGSA Weed Control Efficacy 28 DAT Product RateAMARE ABUTH DIGSA Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84092.5 7.5 100.0 410P9M 1260 96.3 10.0 98.8 DUAL MAGNUM 930 94.5 11.3100.0 DUAL MAGNUM 1400 95.0 11.3 100.0 COTORAN 4 1120 87.5 26.3 86.3COTORAN 4 1800 88.8 68.8 87.5 VALOR SX 48 60.0 85.0 82.5 VALOR SX 7091.3 100.0 100.0 SENCOR DF 370 96.3 91.3 93.8 SENCOR DF 560 71.3 92.588.8 410P9M 840 100.0 95.0 98.8 VALOR SX 48 410P9M 1260 97.0 90.0 92.5VALOR SX 48 410P9M 840 99.8 93.4 93.9 VALOR SX 70 410P9M 1260 100.0 96.3100.0 VALOR SX 70 410P9M 840 100.0 33.8 99.5 COTORAN 4 1120 410P9M 1260100.0 40.0 100.0 COTORAN 4 1120 410P9M 840 100.0 57.0 100.0 COTORAN 41800 410P9M 1260 100.0 76.3 100.0 COTORAN 4 1800 410P9M 840 100.0 90.0100.0 SENCOR DF 370 410P9M 1260 100.0 90.0 100.0 SENCOR DF 370 410P9M840 100.0 98.8 100.0 SENCOR DF 560 410P9M 1260 97.5 97.5 100.0 SENCOR DF560

The efficacy of the same formulations on prickly sida (SIDSP), hempsesbania (SEBEX) and sicklepod (CASOB) by preemergent application on thesame day as planting the crop was also determined with the resultsreported in the table below.

TABLE SIDSP, SEBEX and CASOB Weed Control Efficacy 28 DAT Product RateSIDSP SEBEX CASOB Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84021.3 10.0 8.8 410P9M 1260 26.3 21.3 20.0 DUAL MAGNUM 930 16.3 12.5 15.0DUAL MAGNUM 1400 23.8 30.0 23.8 COTORAN 4 1120 73.3 47.8 30.8 COTORAN 41800 91.3 59.3 50.0 VALOR SX 48 83.8 64.5 25.0 VALOR SX 70 100.0 66.832.5 SENCOR DF 370 87.0 58.3 57.0 SENCOR DF 560 85.0 56.3 55.0 410P9M840 92.5 67.0 51.3 VALOR SX 48 410P9M 1260 82.5 73.8 47.0 VALOR SX 48410P9M 840 100.0 84.9 58.3 VALOR SX 70 410P9M 1260 100.0 74.0 55.8 VALORSX 70 410P9M 840 70.8 57.5 36.0 COTORAN 4 1120 410P9M 1260 83.8 64.542.8 COTORAN 4 1120 410P9M 840 77.5 65.8 52.5 COTORAN 4 1800 410P9M 126083.8 68.8 61.8 COTORAN 4 1800 410P9M 840 93.8 71.3 55.8 SENCOR DF 370410P9M 1260 95.0 68.8 60.0 SENCOR DF 370 410P9M 840 100.0 76.5 75.0SENCOR DF 560 410P9M 1260 100.0 79.0 74.5 SENCOR DF 560

The efficacy of the same formulations on barnyardgrass (ECHCG) bypreemergent application on the same day as planting the crop was alsodetermined with the results reported in the table below.

TABLE ECHCG Weed Control Efficacy 28 DAT Product Rate ECHCG Formulationg AI/ha 28 DAT 410P9M 840 98.8 410P9M 1260 100.0 DUAL MAGNUM 930 100.0DUAL MAGNUM 1400 100.0 COTORAN 4 1120 100.0 COTORAN 4 1800 100.0 VALORSX 48 100.0 VALOR SX 70 97.5 SENCOR DF 370 100.0 SENCOR DF 560 88.8410P9M 840 100.0 VALOR SX 48 410P9M 1260 97.5 VALOR SX 48 410P9M 840100.0 VALOR SX 70 410P9M 1260 97.5 VALOR SX 70 410P9M 840 100.0 COTORAN4 1120 410P9M 1260 100.0 COTORAN 4 1120 410P9M 840 100.0 COTORAN 4 1800410P9M 1260 100.0 COTORAN 4 1800 410P9M 840 100.0 SENCOR DF 370 410P9M1260 100.0 SENCOR DF 370 410P9M 840 100.0 SENCOR DF 560 410P9M 1260100.0 SENCOR DF 560

The encapsulated acetochlor formulation 410P9M alone exhibited greaterthan 98.8% control of crabgrass (DIGSA) and barnyardgrass (ECHCG) and92.5% or greater control in tank mixes with COTORAN 4, VALOR SX orSENCOR DF at all rate combinations evaluated 28 DAT. Amaranth (AMARE)control efficacy was greater than 92.5% with the encapsulated acetochlorformulation 410P9M alone and greater than 97.0% with tank mixes offormulation 410P9M with VALOR SX, COTORAN 4 or SENCOR DF at the ratesevaluated in this trial. VALOR SX>SENCOR DF>COTORAN 4 for prickly sida(SIDSP) control efficacy as individual products at 28 DAT. Tank mixcombinations of the encapsulated acetochlor formulation 410P9M withSENCOR DF exhibited greater control than tank mixes of 410P9M with VALORSX in this trial 28 DAT with respect to SIDSP. Neither hemp sesbania(SEBEX) nor sicklepod (CASOB) were controlled to acceptable levels inthis trial at 28 DAT.

Example 6. Field Trial Study of Weed Control Efficacy and Soybean andCotton Safety in Preemergent Crop Application of MicroencapsulatedAcetochlor Formulations and Tank Mixtures with Other Herbicides

Aqueous dispersions of microencapsulated acetochlor formulation 410P9Mprepared in Example 2, alone and in tank mix combination with COBRA(lactofen), SPARTAN 4L (sulfentrazone) and PROWL (pendimethalin) weretested on glyphosate-tolerant ROUNDUP READY Flex Cotton or ROUNDUP READYSoy and various weeds. All treatments were applied to soil seeded withROUNDUP READY soybeans or ROUNDUP READY Flex Cotton on the same day asplanting the crop and the associated crop injury was evaluated. Theresults from three field trials are reported in the tables below.

TABLE RR Flex Cotton % Crop Injury 14 DAT in Three Field Trials RateTrial Trial Trial Product g 2010530040 2010530041 2010530042 FormulationAI/ha % GR % SR % GR % SR % GR % SR 410P9M 840 2.0 0.0 0.0 0.0 7.0 3.8410P9M 1260 0.0 0.0 0.0 0.0 15.8 7.5 COBRA 175 0.0 0.0 1.3 0.0 66.3 47.5COBRA 262 3.8 2.0 6.3 0.0 88.8 86.3 SPARTAN 4L 233 80.0 73.8 94.8 94.887.5 76.3 SPARTAN 4L 350 99.8 99.8 100.0 100.0 97.5 96.3 PROWL 1120 0.00.0 1.3 0.0 21.3 10.0 PROWL 1680 0.0 0.0 7.5 0.0 46.3 8.8 410P9M 840 3.32.5 2.5 0.0 78.8 75.0 COBRA 175 410P9M 1260 2.5 0.0 6.3 0.0 82.5 67.5COBRA 175 410P9M 840 3.8 1.3 8.3 0.0 87.5 86.3 COBRA 262 410P9M 1260 8.32.5 8.8 0.0 90.0 83.8 COBRA 262 410P9M 840 85.0 80.0 90.0 90.0 86.3 81.3SPARTAN 4L 233 410P9M 1260 97.5 97.5 93.8 93.8 91.3 87.5 SPARTAN 4L 233410P9M 840 95.8 95.8 99.8 99.8 93.8 91.3 SPARTAN 4L 350 410P9M 1260 98.598.5 100.0 100.0 96.3 96.3 SPARTAN 4L 350 410P9M 840 1.3 0.0 6.3 0.025.0 10.0 PROWL 1120 410P9M 1260 3.8 0.0 6.3 0.0 36.3 10.0 PROWL 1120410P9M 840 2.5 0.0 10.0 0.0 47.5 15.0 PROWL 1680 410P9M 1260 4.5 1.316.3 0.0 58.8 13.8 PROWL 1680

TABLE RR Soybean % Crop Injury 14 DAT in Three Field Trials Trial TrialTrial Rate 2010530040 2010530041 2010530042 Product g % % LF % LF % % LFFormulation AI/ha GR Crinkle % GR Crinkle GR Crinkle 410P9M 840 0.0 0.80.0 3.8 8.3 7.5 410P9M 1260 0.0 1.5 1.3 7.0 16.3 8.8 COBRA 175 0.0 0.00.0 0.0 6.3 0.0 COBRA 262 0.0 0.8 0.0 0.0 20.8 1.3 SPARTAN 233 0.0 0.00.0 0.0 16.3 0.0 4L SPARTAN 350 0.0 0.0 5.0 0.8 33.8 0.0 4L PROWL 11200.0 0.0 0.0 0.8 21.3 1.3 PROWL 1680 0.0 0.0 0.0 0.0 45.0 2.5 410P9M 8400.0 2.0 1.3 6.5 30.0 15.0 COBRA 175 410P9M 1260 0.0 2.8 1.3 10.0 30.017.5 COBRA 175 410P9M 840 0.0 2.5 1.3 4.5 36.3 16.3 COBRA 262 410P9M1260 0.0 5.8 0.0 8.8 35.0 17.5 COBRA 262 410P9M 840 0.0 0.0 1.3 4.5 18.37.5 SPARTAN 233 4L 410P9M 1260 0.0 3.0 0.0 5.3 23.8 9.5 SPARTAN 233 4L410P9M 840 0.0 2.0 1.3 2.5 27.5 7.0 SPARTAN 350 4L 410P9M 1260 0.0 0.80.0 5.0 35.0 8.8 SPARTAN 350 4L 410P9M 840 0.0 0.0 0.0 2.8 27.5 10.8PROWL 1120 410P9M 1260 0.0 5.0 0.0 7.5 32.5 12.5 PROWL 1120 410P9M 8400.0 1.5 0.0 6.3 52.5 25.0 PROWL 1680 410P9M 1260 0.0 3.8 5.0 7.5 53.828.8 PROWL 1680

No significant differences were observed in either growth reduction (%GR) or stand reduction (% SR) for RR Flex Cotton with formulations ofthe encapsulated acetochlor formulation 410P9M, COBRA (lactofen) orPROWL (pendimethalin) in field trials 2010530040 and 2010530041 at therates evaluated in these trials. SPARTAN 4L (sulfentrazone) appliedpreemergent caused between 80.0-100.0% growth reduction and between73.8-100.0% stand reduction compared to untreated rows when used aloneor when tank mixed with the encapsulated acetochlor formulation 410P9M.This injury was not unexpected as the product is not labeled for use incotton. Tank mix combinations of the encapsulated acetochlor formulation410P9M with COBRA at all rate combinations showed less than 8.8% growthreduction and less than 2.5% stand reduction of RR Flex Cotton. Theencapsulated acetochlor formulation 410P9M in tank mixtures with PROWLshowed a 10% or less growth reduction at all but the highest applicationrate and 1.3% or less stand reduction.

RR Soybeans exhibited 5.0% or less growth reduction with any individualproduct or tank mix combination in these trials and leaf crinkle was10.0% or less.

In field trial 2010530042, RR Flex Cotton was more severely injured inthis trial compared to the previous trials with only the low rate of theencapsulated acetochlor formulation 410P9M (840 g ai/ha) havingacceptable levels of growth reduction (7.0%) and stand reduction (3.8%).As in previous trials, SPARTAN 4L caused severe cotton injury both aloneand as a tank mix partner with the encapsulated acetochlor formulation410P9M. In this trial, COBRA also caused a high degree of injury tocotton both alone and as a tank mix partner with the encapsulatedacetochlor formulation 410P9M.

RR Soybean injury was higher in this trial compared to the previoustrials with the encapsulated acetochlor formulation 410P9M and COBRAhaving slightly less injury than SPARTAN 4L or PROWL. The tank mixcombinations of the encapsulated acetochlor formulation 410P9M withPROWL tended to have slightly greater growth reductions than those ofthe encapsulated acetochlor formulation 410P9M with COBRA or withSPARTAN 4L.

The increased injury in this trial compared to the previous trials ismost likely caused by the higher temperatures and humidity when thistrial was initiated. Planting soybeans in these types of conditions isnot a typical grower practice so the level of injury observed in thistrial would not be considered typical.

The efficacy of the same formulations on morningglory (IPOHE),amaranthus (AMASS) and sicklepod (CASOB) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE IPOHE, AMASS and CASOB Weed Control Efficacy 28 and 56 DAT IPOHEIPOHE AMASS AMASS CASOB CASOB Product Rate 28 56 28 56 28 56 Formulationg AI/ha DAT DAT DAT DAT DAT DAT 410P9M 840 0.0 0.0 100.0 65.0 28.8 5.0410P9M 1260 15.0 0.0 100.0 87.5 27.5 26.3 COBRA 175 3.8 0.0 85.0 0.011.3 0.0 COBRA 262 20.0 12.5 62.5 0.0 48.8 25.0 SPARTAN 4L 233 99.8 95.0100.0 73.8 21.3 0.0 SPARTAN 4L 350 100.0 99.8 100.0 100.0 30.0 10.0PROWL 1120 15.0 16.3 100.0 42.5 30.8 18.8 PROWL 1680 17.5 0.0 92.5 42.528.8 0.0 410P9M 840 11.3 12.5 90.0 85.0 18.8 0.0 COBRA 175 410P9M 126020.0 0.0 100.0 100.0 20.0 0.0 COBRA 175 410P9M 840 8.8 0.0 100.0 90.022.5 0.0 COBRA 262 410P9M 1260 6.3 0.0 100.0 100.0 35.0 0.0 COBRA 262410P9M 840 100.0 96.3 100.0 100.0 16.3 5.0 SPARTAN 4L 233 410P9M 1260100.0 96.3 100.0 100.0 30.0 17.5 SPARTAN 4L 233 410P9M 840 100.0 93.5100.0 100.0 32.5 11.3 SPARTAN 4L 350 410P9M 1260 100.0 100.0 100.0 100.033.8 35.0 SPARTAN 4L 350 410P9M 840 8.8 0.0 100.0 85.0 3.8 0.0 PROWL1120 410P9M 1260 8.8 0.0 100.0 92.5 32.5 37.5 PROWL 1120 410P9M 840 30.030.0 100.0 92.5 23.8 12.5 PROWL 1680 410P9M 1260 32.5 10.0 100.0 100.027.5 10.0 PROWL 1680

All formulations in this trial except COBRA alone provided 90% orgreater control of AMASS. The encapsulated acetochlor formulation 410P9Min combination with SPARTAN 4L provided 100% control of IPOHE.

The efficacy of the same formulations on velvetleaf (ABUTH),barnyardgrass (ECHCG) and signalgrass (BRAPP) by preemergent applicationon the same day as planting the crop was also determined with theresults reported in the table below.

TABLE ABUTH, ECHCG and BRAPP Weed Control Efficacy 28 and 56 DAT ABUTHABUTH ECHCG ECHCG BRAPP Product Rate 28 56 28 56 28 BRAPP Formulation gAI/ha DAT DAT DAT DAT DAT 56 DAT 410P9M 840 0.0 5.0 70.0 28.8 37.5 0.0410P9M 1260 0.0 0.0 82.5 90.0 42.5 0.0 COBRA 175 0.0 0.0 45.0 0.0 0.00.0 COBRA 262 0.0 0.0 52.5 25.0 0.0 0.0 SPARTAN 4L 233 86.3 62.5 77.55.0 15.0 0.0 SPARTAN 4L 350 97.5 93.8 96.3 57.5 31.3 25.0 PROWL 112018.8 0.0 97.5 100.0 70.0 37.5 PROWL 1680 36.3 5.0 97.5 87.5 92.5 75.0410P9M 840 5.0 0.0 97.5 87.5 15.0 0.0 COBRA 175 410P9M 1260 5.0 0.0100.0 87.5 36.3 20.0 COBRA 175 410P9M 840 7.5 0.0 77.5 65.0 21.3 0.0COBRA 262 410P9M 1260 10.0 0.0 100.0 100.0 20.0 0.0 COBRA 262 410P9M 84078.8 48.8 98.8 75.0 36.3 21.3 SPARTAN 4L 233 410P9M 1260 85.0 81.3 100.0100.0 61.3 25.0 SPARTAN 4L 233 410P9M 840 67.5 53.8 99.8 86.3 68.8 22.5SPARTAN 4L 350 410P9M 1260 88.8 82.5 100.0 87.5 55.0 21.3 SPARTAN 4L 350410P9M 840 17.5 0.0 65.0 87.5 50.0 18.8 PROWL 1120 410P9M 1260 26.3 0.096.3 92.5 82.5 27.5 PROWL 1120 410P9M 840 37.5 27.5 100.0 100.0 97.595.0 PROWL 1680 410P9M 1260 45.0 27.5 92.5 82.5 87.5 70.0 PROWL 1680

The encapsulated acetochlor formulation 410P9M in certain combinationswith COBRA, SPARTAN 4L or PROWL provided as much as 100% control ofECHCG.

The efficacy of the same formulations on amaranthus (AMASS), velvetleaf(ABUTH) and morningglory (IPOHE) by preemergent application on the sameday as planting the crop was also determined with the results reportedin the table below.

TABLE AMASS, ABUTH and IPOHE Weed Control Efficacy 28 DAT Product RateAMASS ABUTH IPOHE Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 840100.0 16.3 7.5 410P9M 1260 100.0 18.8 7.5 COBRA 175 100.0 22.5 17.5COBRA 262 100.0 21.3 15.0 SPARTAN 4L 233 91.3 60.0 70.0 SPARTAN 4L 350100.0 96.3 92.5 PROWL 1120 100.0 75.0 12.5 PROWL 1680 100.0 97.5 30.0410P9M 840 100.0 26.3 12.5 COBRA 175 410P9M 1260 100.0 25.0 17.5 COBRA175 410P9M 840 100.0 40.0 32.5 COBRA 262 410P9M 1260 100.0 33.8 27.5COBRA 262 410P9M 840 100.0 68.8 85.0 SPARTAN 4L 233 410P9M 1260 100.077.5 91.3 SPARTAN 4L 233 410P9M 840 100.0 85.8 95.8 SPARTAN 4L 350410P9M 1260 100.0 98.8 99.5 SPARTAN 4L 350 410P9M 840 100.0 84.5 21.3PROWL 1120 410P9M 1260 100.0 82.0 25.0 PROWL 1120 410P9M 840 87.5 100.042.5 PROWL 1680 410P9M 1260 100.0 99.5 37.5 PROWL 1680

The encapsulated acetochlor formulation 410P9M in combination withCOBRA, SPARTAN 4L, or PROWL provided 87.5-100% control of AMASS. Theencapsulated acetochlor formulation 410P9M in combination with SPARTAN4L provided 68.8-98.8% control of ABUTH and 85.0 to 99.5% control ofIPOHE.

The efficacy of the same formulations on sicklepod (CASOB), hempsesbania (SEBEX) and barnyardgrass (ECHCG) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE CASOB, SEBEX and ECHCG Weed Control Efficacy 28 DAT Product RateCASOB SEBEX ECHCG Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 8408.8 8.8 87.5 410P9M 1260 23.8 18.8 100.0 COBRA 175 12.5 10.0 75.0 COBRA262 26.3 23.8 68.8 SPARTAN 4L 233 25.0 3.8 80.0 SPARTAN 4L 350 15.0 23.8100.0 PROWL 1120 21.3 7.5 100.0 PROWL 1680 22.5 16.3 100.0 410P9M 84020.0 50.0 100.0 COBRA 175 410P9M 1260 32.0 55.0 100.0 COBRA 175 410P9M840 32.5 57.5 95.0 COBRA 262 410P9M 1260 31.3 67.5 100.0 COBRA 262410P9M 840 18.8 30.0 100.0 SPARTAN 4L 233 410P9M 1260 26.3 42.5 100.0SPARTAN 4L 233 410P9M 840 33.8 50.0 100.0 SPARTAN 4L 350 410P9M 126028.8 56.3 91.3 SPARTAN 4L 350 410P9M 840 23.8 12.5 100.0 PROWL 1120410P9M 1260 28.8 26.3 100.0 PROWL 1120 410P9M 840 28.8 28.8 100.0 PROWL1680 410P9M 1260 38.8 37.5 100.0 PROWL 1680

The encapsulated acetochlor formulation 410P9M in combination withCOBRA, SPARTAN 4L or PROWL provide 91.3% or greater control of ECHCG. Noherbicide alone or in combination provided greater than 38.8% control ofCASOB or greater than 67.5% control of SEBEX.

The efficacy of the same formulations on crowfootgrass (DTTAE),signalgrass (BRAPP) and goosegrass (ELEIN) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE DTTAE, BRAPP and ELEIN Weed Control Efficacy 28 DAT Product RateDTTAE BRAPP ELEIN Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 840100.0 82.5 100.0 410P9M 1260 92.5 88.8 100.0 COBRA 175 57.5 0.0 100.0COBRA 262 45.0 0.0 100.0 SPARTAN 4L 233 92.5 22.5 95.0 SPARTAN 4L 35098.8 100.0 100.0 PROWL 1120 100.0 72.5 100.0 PROWL 1680 100.0 62.5 100.0410P9M 840 100.0 70.0 100.0 COBRA 175 410P9M 1260 100.0 87.5 100.0 COBRA175 410P9M 840 90.0 81.3 92.5 COBRA 262 410P9M 1260 87.5 93.8 100.0COBRA 262 410P9M 840 100.0 97.5 100.0 SPARTAN 4L 233 410P9M 1260 92.5100.0 92.5 SPARTAN 4L 233 410P9M 840 96.3 100.0 100.0 SPARTAN 4L 350410P9M 1260 100.0 100.0 100.0 SPARTAN 4L 350 410P9M 840 92.5 96.3 100.0PROWL 1120 410P9M 1260 100.0 85.0 100.0 PROWL 1120 410P9M 840 100.0 93.8100.0 PROWL 1680 410P9M 1260 93.8 92.5 100.0 PROWL 1680

The encapsulated acetochlor formulation 410P9M both alone and incombination with COBRA, SPARTAN 4L or PROWL provided at least 92.5%control of ELEIN.

The encapsulated acetochlor formulation 410P9M in combination withSPARTAN 4L provided at least 97.5% control of BRAPP.

The efficacy of the same formulations on amaranth (AMARE), velvetleaf(ABUTH) and crabgrass (DIGSA) by preemergent application on the same dayas planting the crop was also determined with the results reported inthe table below.

TABLE AMARE, ABUTH and DIGSA Weed Control Efficacy at 28 DAT ProductRate AMARE ABUTH DIGSA Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M840 70.0 7.5 100.0 410P9M 1260 92.5 3.8 100.0 COBRA 175 35.0 38.8 71.3COBRA 262 55.0 63.8 62.5 SPARTAN 4L 233 100.0 44.5 77.5 SPARTAN 4L 350100.0 70.0 75.0 PROWL 1120 32.5 63.8 90.0 PROWL 1680 33.8 80.0 88.8410P9M 840 75.0 50.0 91.3 COBRA 175 410P9M 1260 81.3 51.3 90.0 COBRA 175410P9M 840 90.0 58.3 91.3 COBRA 262 410P9M 1260 69.5 60.0 100.0 COBRA262 410P9M 840 100.0 47.5 100.0 SPARTAN 4L 233 410P9M 1260 100.0 70.0100.0 SPARTAN 4L 233 410P9M 840 100.0 58.8 91.3 SPARTAN 4L 350 410P9M1260 100.0 100.0 100.0 SPARTAN 4L 350 410P9M 840 63.8 72.5 100.0 PROWL1120 410P9M 1260 91.3 72.5 100.0 PROWL 1120 410P9M 840 82.5 75.0 100.0PROWL 1680 410P9M 1260 100.0 85.0 100.0 PROWL 1680

DIGSA was controlled at least 90% at all rates of tank mixtures of theencapsulated acetochlor formulation 410P9M and COBRA, SPARTAN 4L, orPROWL. AMARE was controlled most effectively with SPARTAN alone and intank mixtures with the encapsulated acetochlor formulation 410P9M andwith PROWL in tank mixtures at the highest rate tested.

The efficacy of the same formulations on prickly sida (SIDSP), hempsesbania (SEBEX) and sicklepod (CASOB) by preemergent application on thesame day as planting the crop was also determined with the resultsreported in the table below.

TABLE SIDSP, SEBEX and CASOB Weed Control Efficacy 28 DAT Product RateSIDSP SEBEX CASOB Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84015.0 0.0 12.5 410P9M 1260 25.0 18.8 15.0 COBRA 175 17.5 27.5 21.3 COBRA262 31.3 36.3 33.8 SPARTAN 4L 233 65.0 25.0 16.3 SPARTAN 4L 350 80.036.3 17.5 PROWL 1120 62.5 12.5 23.8 PROWL 1680 70.0 23.8 31.3 410P9M 840COBRA 175 47.5 43.8 32.5 410P9M 1260 COBRA 175 56.3 52.8 45.0 410P9M 840COBRA 262 63.8 45.0 38.3 410P9M 1260 COBRA 262 63.8 50.8 38.8 410P9M 840SPARTAN 4L 233 92.5 35.0 15.0 410P9M 1260 SPARTAN 4L 233 95.0 52.0 18.8410P9M 840 SPARTAN 4L 350 93.8 50.0 21.3 410P9M 1260 SPARTAN 4L 350 97.567.5 23.8 410P9M 840 PROWL 1120 63.3 27.5 23.8 410P9M 1260 PROWL 112083.8 43.8 26.3 410P9M 840 PROWL 1680 88.8 26.3 27.5 410P9M 1260 PROWL1680 90.0 41.3 34.5

Tank mixtures of the encapsulated acetochlor formulation 410P9M andSPARTAN 4L showed commercially acceptable levels of weed control inSIDSP. Neither SEBEX nor CASOB were effectively controlled in this trialwith a single herbicide treatment or with a mixture of two herbicides.

The efficacy of the same formulations on barnyardgrass (ECHCG) bypreemergent application on the same day as planting the crop was alsodetermined with the results reported in the table below.

TABLE ECHCG Weed Control Efficacy 28 DAT Product Rate ECHCG Formulationg AI/ha 28 DAT 410P9M 840 97.5 410P9M 1260 100.0 COBRA 175 62.5 COBRA262 82.5 SPARTAN 4L 233 100.0 SPARTAN 4L 350 100.0 PROWL 1120 100.0PROWL 1680 100.0 410P9M 840 COBRA 175 100.0 410P9M 1260 COBRA 175 100.0410P9M 840 COBRA 262 97.5 410P9M 1260 95.0 COBRA 262 410P9M 840 SPARTAN4L 233 100.0 410P9M 1260 SPARTAN 4L 233 100.0 410P9M 840 SPARTAN 4L 350100.0 410P9M 1260 SPARTAN 4L 350 100.0 410P9M 840 PROWL 1120 100.0410P9M 1260 PROWL 1120 100.0 410P9M 840 PROWL 1680 100.0 410P9M 1260PROWL 1680 100.0

All tank mixtures of the encapsulated acetochlor formulation 410P9Mshowed commercially acceptable levels of weed control of ECHCG.

Example 7. Field Trial Study of Weed Control Efficacy and Soybean andCotton Safety in Preemergent Crop Application of MicroencapsulatedAcetochlor Formulations and Tank Mixtures with Other Herbicides

Aqueous dispersions of microencapsulated acetochlor formulation 410P9Mprepared in Example 2, alone and in tank mix combination with GOAL 2XL(oxyfluorfen), REFLEX (fomesafen), or SHARPEN (saflufenacil) were testedon glyphosate-tolerant ROUNDUP READY Flex Cotton or ROUNDUP READY Soyand various weeds. All treatments were applied to soil seeded withROUNDUP READY soybeans or ROUNDUP READY Flex Cotton on the same day asplanting and the associated crop injury was evaluated. The results fromthree field trials are reported in the tables below.

TABLE RR Flex Cotton % Crop Injury 14 DAT in Three Field Trials TrialTrial Trial Product Rate 2010530043 2010530044 2010530045 Formulation gAI/ha % GR % SR % GR % SR % GR % SR 410P9M 840 1.3 0.0 6.8 0.0 12.5 6.3410P9M 1260 2.5 1.3 18.8 0.0 16.3 12.5 GOAL 2XL 188 0.0 0.0 41.3 2.525.0 16.3 GOAL 2XL 280 0.0 0.0 47.5 6.3 35.0 17.5 REFLEX 280 0.0 1.3 0.00.0 7.5 1.3 REFLEX 420 7.5 5.0 3.8 1.3 12.5 7.5 SHARPEN 16.8 0.0 0.0 0.00.0 6.3 5.0 SHARPEN 24.7 0.0 0.0 1.3 0.0 11.3 7.5 410P9M 840 0.0 2.047.5 5.0 28.8 15.0 GOAL 2XL 188 410P9M 1260 0.0 1.3 46.3 6.3 28.8 16.3GOAL 2XL 188 410P9M 840 2.5 1.3 55.0 8.8 42.5 18.8 GOAL 2XL 280 410P9M1260 0.0 0.0 53.8 13.8 45.0 15.0 GOAL 2XL 280 410P9M 840 1.3 2.5 10.81.3 15.3 8.8 REFLEX 280 410P9M 1260 0.0 3.8 27.5 7.5 22.5 13.8 REFLEX280 410P9M 840 2.5 1.3 31.3 10.0 23.3 15.0 REFLEX 420 410P9M 1260 1.32.5 40.0 11.3 26.3 13.8 REFLEX 420 410P9M 840 0.0 0.0 10.3 5.0 17.5 13.8SHARPEN 16.8 410P9M 1260 0.0 0.0 16.3 5.0 18.8 13.8 SHARPEN 16.8 410P9M840 0.0 0.0 18.8 10.0 11.3 11.3 SHARPEN 24.7 410P9M 1260 1.3 2.5 20.88.8 27.5 15.0 SHARPEN 24.7

TABLE RR Soybean % Crop Injury 14 DAT in Three Field Trials Trial TrialTrial Rate 2010530043 2010530044 2010530045 Product g % % LF % % LF % %LF Formulation AI/ha GR Crinkle GR Crinkle GR Crinkle 410P9M 840 0.0 0.81.3 5.3 13.8 8.8 410P9M 1260 0.0 2.3 8.8 9.3 15.0 13.8 GOAL 2XL 188 0.00.8 30.0 7.5 27.5 4.5 GOAL 2XL 280 0.0 0.8 45.0 11.3 41.3 8.3 REFLEX 2800.0 0.0 1.3 0.0 2.5 0.0 REFLEX 420 0.0 0.0 3.8 0.0 7.5 0.0 SHARPEN 16.80.0 0.0 1.3 0.0 17.5 0.0 SHARPEN 24.7 0.0 0.0 1.3 0.0 28.8 0.0 410P9M840 GOAL 2XL 188 0.0 7.8 45.0 16.3 35.0 13.8 410P9M 1260 GOAL 2XL 1880.0 6.0 41.3 22.5 45.0 18.8 410P9M 840 GOAL 2XL 280 0.0 7.0 57.5 22.551.3 17.5 410P9M 1260 GOAL 2XL 280 0.0 9.8 58.8 28.8 48.8 15.8 410P9M840 REFLEX 280 0.0 2.8 3.8 6.3 21.3 14.5 410P9M 1260 REFLEX 280 0.0 5.36.3 8.8 20.0 17.5 410P9M 840 REFLEX 420 0.0 2.5 5.0 8.3 16.3 13.8 410P9M1260 REFLEX 420 0.0 3.5 3.8 11.3 20.0 15.0 410P9M 840 SHARPEN 16.8 0.02.0 10.0 6.3 25.0 12.5 410P9M 1260 SHARPEN 16.8 0.0 2.3 7.5 9.5 33.315.0 410P9M 840 SHARPEN 24.7 0.0 0.8 7.5 7.5 35.0 10.8 410P9M 1260SHARPEN 24.7 0.0 2.3 21.3 8.8 37.5 18.8

In Field Trial 2010530043, RR Flex Cotton growth exhibited a slightreduction in growth (7.5%) with preemergent applications of REFLEX(fomesafen) at 420 g ai/ha. All other treatments with formulations ofthe encapsulated acetochlor formulation 410P9M, GOAL 2XL (oxyfluorfen),low rate of REFLEX (fomesafen), or SHARPEN (saflufenacil) at the ratesevaluated in this trial had less than 2.5% growth reduction. Nosignificant differences in cotton stand reduction were observed in thistrial.

RR Soybeans had no growth reduction from the individual treatments ortank mix combinations. The combination of the encapsulated acetochlorformulation 410P9M and GOAL 2XL had the greatest % Leaf crinkle in thistrial between 6.0 and 9.8%, which was significantly greater than theindividual products.

In Field Trial 2010530044, RR Flex Cotton growth was impacted the leastby low rate application of formulations of the encapsulated acetochlorformulation 410P9M (840 g ai/ha) and both rates of REFLEX (fomesafen)and SHARPEN (saflufenacil). GOAL 2XL (oxyfluorfen) and tank mixes of theencapsulated acetochlor formulation 410P9M with GOAL 2XL had growthreduction between 41.3-55.0%. Stand reduction was lowest forformulations of encapsulated acetochlor formulation 410P9M, REFLEX andSHARPEN, while the tank mix combinations of the encapsulated acetochlorformulation 410P9M with REFLEX or SHARPEN tended to have the greateststand reductions.

RR Soybeans had slight growth reduction from applications ofencapsulated acetochlor formulation 410P9M, REFLEX, SHARPEN and the tankmix combinations of composition 410P9M with REFLEX or SHARPEN. GOAL 2XLand tank mix combinations of the encapsulated acetochlor formulation410P9M with GOAL 2XL had growth reduction between 30-58.8% in thistrial. Leaf crinkle was greatest for tank mix combinations ofcomposition 410P9M with GOAL 2XL and least for composition 410P9M tankmixed with REFLEX or SHARPEN.

In Field Trial 2010530045, RR Flex Cotton growth reduction ranged from6.3% to 45.0% for all treatments. Tank mixes of the encapsulatedacetochlor formulation 410P9M in combination with GOAL 2XL had thehighest % growth reduction in this trial. A similar trend was identifiedin % stand reduction with REFLEX and SHARPEN having the least and GOAL2XL having the greatest impact on RR Flex Cotton.

For RR Soybeans, REFLEX<the encapsulated acetochlor formulation410P9M<SHARPEN<GOAL 2XL with respect to growth reduction as individualproducts. The tank mix combination of composition 410P9M with GOAL 2XLhad the greatest % growth reduction, while composition 410P9M tank mixedwith REFLEX had the least. No leaf crinkle was observed with eitherREFLEX or SHARPEN and a slight amount was detected with GOAL 2XL. Thetank mix combinations of the encapsulated acetochlor formulation 410P9Mwith GOAL 2XL or REFLEX or SHARPEN had less than 18.8% leaf crinkle inthis trial.

This trial was initiated when temperatures and humidity are much higherthan typically found during cotton or soybean planting time. Theseconditions can promote rapid crop growth and uptake of herbicides thuscausing elevated amounts of crop injury not typically observed.

The efficacy of the same formulations on morningglory (IPOHE),amaranthus (AMASS) and sicklepod (CASOB) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE IPOHE, AMASS and CASOB Weed Control Efficacy 28 and 56 DAT IPOHEIPOHE AMASS AMASS CASOB CASOB Product Rate 28 56 28 56 28 56 Formulationg AI/ha DAT DAT DAT DAT DAT DAT 410P9M 840 0.0 0.0 100.0 85.0 38.8 17.5410P9M 1260 3.8 0.0 87.5 75.0 27.5 5.0 GOAL 2XL 188 5.0 0.0 100.0 25.042.5 17.5 GOAL 2XL 280 3.8 0.0 100.0 17.5 20.0 0.0 REFLEX 280 17.5 17.5100.0 96.3 30.0 6.3 REFLEX 420 17.5 0.0 100.0 75.0 20.0 0.0 SHARPEN 16.817.5 0.0 25.0 0.0 0.0 0.0 SHARPEN 24.7 12.5 12.5 36.3 0.0 13.8 0.0410P9M 840 0.0 0.0 100.0 100.0 10.0 0.0 GOAL 2XL 188 410P9M 1260 7.5 0.0100.0 100.0 31.3 5.0 GOAL 2XL 188 410P9M 840 3.8 5.0 100.0 100.0 23.825.0 GOAL 2XL 280 410P9M 1260 7.5 0.0 100.0 100.0 20.0 0.0 GOAL 2XL 280410P9M 840 32.5 17.5 100.0 100.0 38.8 17.5 REFLEX 280 410P9M 1260 13.810.0 100.0 100.0 41.3 12.5 REFLEX 280 410P9M 840 38.8 43.8 100.0 100.022.5 0.0 REFLEX 420 410P9M 1260 41.3 25.0 100.0 100.0 26.3 6.3 REFLEX420 410P9M 840 16.3 17.5 100.0 92.5 22.5 5.0 SHARPEN 16.8 410P9M 126043.8 20.0 100.0 100.0 20.0 0.0 SHARPEN 16.8 410P9M 840 55.0 37.5 100.0100.0 32.5 6.3 SHARPEN 24.7 410P9M 1260 20.0 10.0 100.0 100.0 46.3 25.0SHARPEN 24.7

The encapsulated acetochlor formulation 410P9M provided commerciallyacceptable levels of weed control for AMASS with GOAL 2XL, REFLEX, andSHARPEN as tank mix partners. IPOHE and CASOB were not effectivelycontrolled by any herbicide treatment in this trial.

The efficacy of the same formulations on velvetleaf (ABUTH),barnyardgrass (ECHCG) and signalgrass (BRAPP) by preemergent applicationon the same day as planting the crop was also determined with theresults reported in the table below.

TABLE ABUTH, ECHCG and BRAPP Weed Control Efficacy 28 and 56 DAT ABUTHABUTH ECHCG ECHCG BRAPP BRAPP Product Rate g 28 56 28 56 28 56Formulation AI/ha DAT DAT DAT DAT DAT DAT 410P9M 840 7.5 0.0 82.5 50.018.8 5.0 410P9M 1260 0.0 0.0 100.0 100.0 35.0 0.0 GOAL 2XL 188 11.3 0.072.5 25.0 36.3 0.0 GOAL 2XL 280 10.0 0.0 61.3 17.5 22.5 0.0 REFLEX 28021.3 5.0 50.0 35.0 0.0 0.0 REFLEX 420 20.0 0.0 53.8 10.0 5.0 0.0 SHARPEN16.8 8.8 0.0 0.0 0.0 0.0 0.0 SHARPEN 24.7 11.3 0.0 0.0 0.0 0.0 0.0410P9M 840 16.3 0.0 97.5 80.0 60.0 30.0 GOAL 2XL 188 410P9M 1260 17.50.0 97.5 75.0 72.5 25.0 GOAL 2XL 188 410P9M 840 21.3 10.0 100.0 100.037.5 5.0 GOAL 2XL 280 410P9M 1260 25.0 5.0 97.5 100.0 57.5 0.0 GOAL 2XL280 410P9M 840 26.3 10.0 97.5 87.5 35.0 5.0 REFLEX 280 410P9M 1260 20.07.5 100.0 100.0 40.0 0.0 REFLEX 280 410P9M 840 47.5 47.5 100.0 92.5 26.30.0 REFLEX 420 410P9M 1260 27.5 5.0 100.0 92.5 76.3 30.0 REFLEX 420410P9M 840 21.3 0.0 65.0 17.5 12.5 5.0 SHARPEN 16.8 410P9M 1260 21.312.5 95.0 100.0 55.0 10.0 SHARPEN 16.8 410P9M 840 38.8 17.5 90.0 85.030.0 5.0 SHARPEN 24.7 410P9M 1260 25.0 5.0 92.5 75.0 38.8 5.0 SHARPEN24.7

Tank mix combinations of the encapsulated acetochlor formulation 410P9Mand REFLEX provided the best control of ECHCG. Some tank mixcombinations of composition 410P9M and SHARPEN and GOAL 2XL alsoprovided acceptable levels of weed control.

The efficacy of the same formulations on amaranthus (AMARE), pricklysida (SIDSP) and velvetleaf (ABUTH) by preemergent application on thesame day as planting the crop was also determined with the resultsreported in the table below.

TABLE AMARE, SIDSP and ABUTH Weed Control Efficacy 28 DAT Product RateAMARE SIDSP ABUTH Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 840100.0 25.0 12.5 410P9M 1260 100.0 56.0 7.5 GOAL 2XL 188 93.8 88.8 95.0GOAL 2XL 280 92.5 95.0 95.0 REFLEX 280 100.0 21.3 15.0 REFLEX 420 100.070.0 23.8 SHARPEN 16.8 35.0 17.5 3.8 SHARPEN 24.7 76.3 35.0 11.3 410P9M840 96.3 92.5 96.3 GOAL 2XL 188 410P9M 1260 100.0 95.0 92.5 GOAL 2XL 188410P9M 840 92.5 95.0 98.8 GOAL 2XL 280 410P9M 1260 98.8 98.8 97.5 GOAL2XL 280 410P9M 840 100.0 87.0 33.8 REFLEX 280 410P9M 1260 100.0 95.836.3 REFLEX 280 410P9M 840 100.0 97.5 36.3 REFLEX 420 410P9M 1260 100.094.5 46.3 REFLEX 420 410P9M 840 100.0 83.8 25.8 SHARPEN 16.8 410P9M 1260100.0 97.5 28.8 SHARPEN 16.8 410P9M 840 100.0 87.5 32.5 SHARPEN 24.7410P9M 1260 100.0 98.8 62.5 SHARPEN 24.7

Tank mixtures of the encapsulated acetochlor formulation 410P9M withGOAL 2XL provided commercially acceptable levels of weed control for allweeds tested in this trial (AMARE, SIDSP and ABUTH). REFLEX and SHARPENalso provided effective weed control for AMARE and SIDSP.

The efficacy of the same formulations on barnyardgrass (ECHCG),morningglory (IPOHE) and crabgrass (DIGSA) by preemergent application onthe same day as planting the crop was also determined with the resultsreported in the table below.

TABLE ECHCG, IPOHE and DIGSA Weed Control Efficacy 28 DAT Product RateECHCG IPOHE DIGSA Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 840100.0 0.0 100.0 410P9M 1260 100.0 7.5 100.0 GOAL 2XL 188 100.0 17.5100.0 GOAL 2XL 280 100.0 36.3 100.0 REFLEX 280 100.0 17.5 97.5 REFLEX420 97.5 11.3 100.0 SHARPEN 16.8 77.5 12.5 62.5 SHARPEN 24.7 91.3 17.572.5 410P9M GOAL 2XL  840 + 188 100.0 20.0 100.0 410P9M GOAL 2XL 1260 +188 100.0 21.3 100.0 410P9M 840 GOAL 2XL 280 100.0 53.8 100.0 410P9M1260 GOAL 2XL 280 100.0 51.3 100.0 410P9M 840 REFLEX 280 100.0 46.3100.0 410P9M 1260 REFLEX 280 100.0 43.8 100.0 410P9M 840 REFLEX 420100.0 46.3 100.0 410P9M 1260 REFLEX 420 100.0 49.5 100.0 410P9M 840SHARPEN 16.8 100.0 38.8 100.0 410P9M 1260 SHARPEN 16.8 100.0 36.3 100.0410P9M 840 SHARPEN 24.7 100.0 61.3 100.0 410P9M 1260 SHARPEN 24.7 100.050.0 100.0

ECHCG and DIGSA were effectively controlled with all tank mixturestested in this trial. IPOHE was not effectively controlled with anyherbicide alone or in combination.

The efficacy of the same formulations on hemp sesbania (SEBEX) andcrowfootgrass (DTTAE) by preemergent application on the same day asplanting the crop was also determined with the results reported in thetable below.

TABLE SEBEX and DTTAE Weed Control Efficacy 28 DAT Product Rate SEBEXDTTAE Formulation g AI/ha 28 DAT 28 DAT 410P9M 840 18.8 100.0 410P9M1260 35.0 100.0 GOAL 2XL 188 51.3 100.0 GOAL 2XL 280 62.5 100.0 REFLEX280 10.0 92.5 REFLEX 420 16.3 100.0 SHARPEN 16.8 3.8 82.5 SHARPEN 24.70.0 90.0 410P9M 840 63.8 100.0 GOAL 2XL 188 410P9M 1260 74.8 100.0 GOAL2XL 188 410P9M 840 68.3 100.0 GOAL 2XL 280 410P9M 1260 67.0 100.0 GOAL2XL 280 410P9M 840 59.0 100.0 REFLEX 280 410P9M 1260 65.8 100.0 REFLEX280 410P9M 840 71.3 100.0 REFLEX 420 410P9M 1260 73.8 100.0 REFLEX 420410P9M 840 40.0 100.0 SHARPEN 16.8 410P9M 1260 50.3 100.0 SHARPEN 16.8410P9M 840 50.0 100.0 SHARPEN 24.7 410P9M 1260 57.0 100.0 SHARPEN 24.7

In this trial, all mixtures tested with 410P9M provided complete controlof DTTAE.

The efficacy of the same formulations on amaranthus (AMARE), velvetleaf(ABUTH) and crabgrass (DIGSA) by preemergent application on the same dayas planting the crop was also determined with the results reported inthe table below.

TABLE AMARE, ABUTH and DIGSA Weed Control Efficacy 28 DAT Product RateAMARE ABUTH DIGSA Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84092.5 10.0 100.0 410P9M 1260 91.3 0.0 100.0 GOAL 2XL 188 40.0 46.3 61.3GOAL 2XL 280 20.0 61.3 75.0 REFLEX 280 100.0 7.5 100.0 REFLEX 420 100.015.0 100.0 SHARPEN 16.8 72.5 18.8 8.8 SHARPEN 24.7 75.0 27.5 10.0 410P9M840 72.5 55.0 100.0 GOAL 2XL 188 410P9M 1260 90.0 60.0 100.0 GOAL 2XL188 410P9M 840 67.5 62.5 87.5 GOAL 2XL 280 410P9M 1260 82.5 70.8 100.0GOAL 2XL 280 410P9M 840 100.0 12.5 100.0 REFLEX 280 410P9M 1260 95.011.3 100.0 REFLEX 280 410P9M 840 100.0 28.8 100.0 REFLEX 420 410P9M 1260100.0 17.5 100.0 REFLEX 420 410P9M 840 90.0 47.0 90.0 SHARPEN 16.8410P9M 1260 100.0 40.0 100.0 SHARPEN 16.8 410P9M 840 92.5 45.0 77.5SHARPEN 24.7 410P9M 1260 100.0 38.8 95.0 SHARPEN 24.7

DIGSA was controlled between 77.5 to 100% for all tank mixtures tested.The encapsulated acetochlor formulation 410P9M in combination withREFLEX showed the greatest control of AMARE and DIGSA. ABUTH was noteffectively controlled with any herbicide in this trial.

The efficacy of the same formulations on prickly sida (SIDSP), hempsesbania (SEBEX) and sicklepod (CASOB) by preemergent application on thesame day as planting the crop was also determined with the resultsreported in the table below.

TABLE SIDSP, SEBEX and CASOB Weed Control Efficacy 28 DAT Product RateSIDSP SEBEX CASOB Formulation g AI/ha 28 DAT 28 DAT 28 DAT 410P9M 84021.3 12.5 21.3 410P9M 1260 20.0 22.5 12.5 GOAL 2XL 188 52.5 27.5 22.5GOAL 2XL 280 62.5 33.8 20.0 REFLEX 280 37.5 17.5 7.5 REFLEX 420 58.831.3 22.5 SHARPEN 16.8 46.3 3.8 3.8 SHARPEN 24.7 43.8 11.3 16.3 410P9M840 63.8 38.3 18.8 GOAL 2XL 188 410P9M 1260 65.0 41.3 27.5 GOAL 2XL 188410P9M 840 66.3 43.8 27.5 GOAL 2XL 280 410P9M 1260 73.8 51.3 30.0 GOAL2XL 280 410P9M 840 80.0 41.3 21.3 REFLEX 280 410P9M 1260 65.0 37.5 20.0REFLEX 280 410P9M 840 75.0 36.3 26.3 REFLEX 420 410P9M 1260 73.8 51.526.3 REFLEX 420 410P9M 840 69.5 27.5 20.0 SHARPEN 16.8 410P9M 1260 75.031.3 12.5 SHARPEN 16.8 410P9M  840 + 24.7 57.5 21.3 18.8 SHARPEN 410P9M1260 + 24.7 78.8 33.8 12.5 SHARPEN

SIDSP, SEBEX and CASOB were not effectively controlled by any treatmentin this trial.

The efficacy of the same formulations on barnyardgrass (ECHCG) bypreemergent application on the same day as planting the crop was alsodetermined with the results reported in the table below.

TABLE ECHCG Weed Control Efficacy 28 DAT Product Rate ECHCG Formulationg AI/ha 28 DAT 410P9M 840 100.0 410P9M 1260 100.0 GOAL 2XL 188 93.8 GOAL2XL 280 82.5 REFLEX 280 92.5 REFLEX 420 100.0 SHARPEN 16.8 67.5 SHARPEN24.7 95.0 410P9M 840 GOAL 2XL 188 100.0 410P9M 1260 GOAL 2XL 188 97.5410P9M 840 GOAL 2XL 280 97.5 410P9M 1260 GOAL 2XL 280 100.0 410P9M 840REFLEX 280 100.0 410P9M 1260 REFLEX 280 97.5 410P9M 840 REFLEX 420 100.0410P9M 1260 REFLEX 420 100.0 410P9M 840 SHARPEN 16.8 96.3 410P9M 1260SHARPEN 16.8 100.0 410P9M 840 SHARPEN 24.7 87.5 410P9M 1260 SHARPEN 24.796.3

In this trial, commercially acceptable levels of weed control wereobserved with all except one rate of the tank mixtures with theencapsulated acetochlor formulation 410P9M.

Example 8. Field Trial Study of Weed Control Efficacy and Soybean andCotton Safety in Preemergent Crop Application of MicroencapsulatedAcetochlor Formulations and Blends

Aqueous dispersions of microencapsulated acetochlor formulations 410P9Mand 403U7N prepared in Example 2, alone and in blended combinations weretested on glyphosate-tolerant ROUNDUP READY Flex Cotton or ROUNDUP READYSoy and various weeds. The commercial formulation DUAL MAGNUM, availablefrom Syngenta and comprising s-metalochlor as the active ingredient andproprietary ingredients was also tested. All treatments were applied tosoil seeded with ROUNDUP READY Flex Cotton or ROUNDUP READY soybeans onthe same day as planting and the associated crop injury was evaluated at14-16 DAT. The results from three field trials are reported in thetables below.

TABLE RR Flex Cotton % Crop Injury 14-16 DAT in Three Field Trials TrialTrial Trial Product Rate 201053034 2010530035 201053036 FormulationRatio g AI/ha % GR % SR % GR % SR % GR % SR 410P9M NA 1260 0.0 0.0 10.07.5 16.3 0.0 410P9M NA 1480 5.0 2.5 15.3 7.5 32.5 5.0 410P9M NA 1820 0.00.0 16.3 6.3 35.0 5.0 403U7N NA 1260 0.0 0.0 10.0 2.5 15.0 3.8 403U7N NA1480 2.5 0.0 17.0 7.5 16.3 2.5 403U7N NA 1820 3.8 0.0 13.0 3.8 22.5 3.8403U7N 25 1260 0.0 1.3 13.3 7.5 20.0 6.3 410P9M 75 403U7N 25 1480 5.01.3 17.5 6.3 25.0 3.8 410P9M 75 403U7N 25 1820 2.5 1.3 20.0 5.0 32.5 0.0410P9M 75 403U7N 50 1260 0.0 1.3 6.3 1.3 18.3 3.8 410P9M 50 403U7N 501480 3.8 2.5 10.8 0.0 25.0 5.0 410P9M 50 403U7N 50 1820 1.3 1.3 17.0 2.531.3 5.0 410P9M 50 403U7N 75 1260 2.5 2.5 12.5 3.8 12.5 1.3 410P9M 25403U7N 75 1480 3.8 2.5 10.0 5.0 25.0 5.0 410P9M 25 403U7N 75 1820 3.81.3 17.0 3.8 31.3 5.0 410P9M 25 DUAL MAGNUM NA 1400 4.5 0.0 2.5 0.0 18.83.8 DUAL MAGNUM NA 1680 13.8 3.8 2.5 1.3 32.5 6.3 DUAL MAGNUM NA 196018.3 5.0 1.3 1.3 33.8 3.8

TABLE RR Soybean % Crop Injury 14-16 DAT in Three Field Trials TrialTrial Trial 2010530034 2010530035 2010530036 Product Rate g % LF % LF %LF Formulation Ratio AI/ha % GR Cupp % GR Crink % GR Crink 410P9M NA1260 0.0 0.0 7.5 16.3 15.0 13.8 410P9M NA 1480 0.0 5.8 11.5 19.5 15.015.0 410P9M NA 1820 0.0 5.3 10.8 21.3 17.5 15.0 403U7N NA 1260 0.0 0.06.3 16.8 15.0 13.8 403U7N NA 1480 0.0 4.5 12.8 22.5 11.3 12.0 403U7N NA1820 0.0 4.5 9.5 23.8 15.0 13.8 403U7N 25 1260 0.0 1.5 10.8 20.8 11.313.8 410P9M 75 403U7N 25 1480 0.0 4.5 20.8 23.3 18.8 13.8 410P9M 75403U7N 25 1820 0.0 4.0 15.0 27.5 17.5 13.8 410P9M 75 403U7N 50 1260 0.02.3 8.8 18.8 10.0 11.3 410P9M 50 403U7N 50 1480 1.3 9.0 9.8 20.8 12.510.0 410P9M 50 403U7N 50 1820 0.0 5.8 15.0 22.5 15.0 13.8 410P9M 50403U7N 75 1260 0.1 1.3 9.3 18.3 8.8 8.8 410P9M 25 403U7N 75 1480 0.0 3.311.3 21.3 16.3 13.8 410P9M 25 403U7N 75 1820 0.0 8.0 13.8 22.5 17.5 15.0410P9M 25 DUAL MAGNUM NA 1400 0.0 0.0 3.3 6.3 13.8 10.8 DUAL MAGNUM NA1680 0.0 4.8 2.5 6.8 13.8 15.0 DUAL MAGNUM NA 1960 0.0 4.5 3.8 5.8 15.012.5

The efficacy of the same encapsulated acetochlor formulations and blendson various weed species by preemergent application on the same day asplanting the crop was also determined. The associated weed control wasevaluated and the results are reported in the tables below.

TABLE IPOHE and AMASS Weed Control Efficacy IPOHE IPOHE IPOHE AMASSAMASS AMASS Product Rate 23 41 57 23 41 57 Formulation Ratio g AI/ha DATDAT DAT DAT DAT DAT 410P9M NA 1260 17.5 10.0 12.5 77.5 55.0 45.0 410P9MNA 1480 13.8 0.0 12.5 100.0 100.0 90.0 410P9M NA 1820 26.3 0.0 0.0 97.5100.0 96.3 403U7N NA 1260 0.0 0.0 0.0 91.3 67.5 75.0 403U7N NA 1480 15.05.0 0.0 100.0 65.0 77.5 403U7N NA 1820 16.3 7.5 0.0 100.0 100.0 100.0403U7N 25 1260 13.8 5.0 0.0 100.0 100.0 92.5 410P9M 75 403U7N 25 14800.0 0.0 0.0 100.0 100.0 100.0 410P9M 75 403U7N 25 1820 10.0 0.0 0.0100.0 100.0 97.5 410P9M 75 403U7N 50 1260 6.3 0.0 0.0 96.3 87.5 80.0410P9M 50 403U7N 50 1480 0.0 0.0 0.0 92.5 75.0 75.0 410P9M 50 403U7N 501820 7.5 0.0 0.0 100.0 100.0 95.0 410P9M 50 403U7N 75 1260 12.5 10.012.5 95.0 80.0 50.0 410P9M 25 403U7N 75 1480 7.5 0.0 0.0 100.0 100.082.5 410P9M 25 403U7N 75 1820 5.0 0.0 0.0 100.0 100.0 100.0 410P9M 25DUAL MAGNUM NA 1400 22.5 15.0 0.0 100.0 87.5 82.5 DUAL MAGNUM NA 168015.0 0.0 0.0 100.0 87.5 77.5 DUAL MAGNUM NA 1960 45.0 12.5 0.0 100.0100.0 100.0

TABLE CASOB and ABUTH Weed Control Efficacy CASOB CASOB CASOB ABUTHABUTH ABUTH Product Rate 23 41 57 23 41 57 Formulation Ratio g AI/ha DATDAT DAT DAT DAT DAT 410P9M NA 1260 32.5 5.0 10.0 3.8 0.0 0.0 410P9M NA1480 22.5 0.0 10.0 16.3 11.3 5.0 410P9M NA 1820 33.8 5.0 0.0 0.0 0.0 0.0403U7N NA 1260 30.0 10.0 0.0 10.0 0.0 0.0 403U7N NA 1480 27.5 12.5 5.011.3 5.0 0.0 403U7N NA 1820 26.3 6.3 0.0 5.0 6.3 0.0 403U7N 25 1260 46.315.0 0.0 2.5 5.0 0.0 410P9M 75 403U7N 25 1480 28.8 5.0 5.0 7.5 5.0 5.0410P9M 75 403U7N 25 1820 37.5 15.0 10.0 2.5 0.0 0.0 410P9M 75 403U7N 501260 18.8 5.0 0.0 5.0 3.8 0.0 410P9M 50 403U7N 50 1480 55.0 35.0 18.86.3 5.0 0.0 410P9M 50 403U7N 50 1820 56.3 32.5 20.0 12.5 0.0 0.0 410P9M50 403U7N 75 1260 23.8 0.0 0.0 2.5 0.0 0.0 410P9M 25 403U7N 75 1480 22.57.5 20.0 0.0 0.0 0.0 410P9M 25 403U7N 75 1820 21.3 6.3 5.0 2.5 6.3 5.0410P9M 25 DUAL MAGNUM NA 1400 35.0 17.5 7.5 55.0 22.5 10.0 DUAL MAGNUMNA 1680 51.3 22.5 20.0 66.3 40.0 25.0 DUAL MAGNUM NA 1960 47.5 20.0 0.067.5 52.5 42.5

TABLE ESHCG and BRAPP Weed Control Efficacy ECHCG ECHCG ECHCG BRAPPBRAPP BRAPP Product Rate 23 41 57 23 41 57 Formulation Ratio g AI/ha DATDAT DAT DAT DAT DAT 410P9M NA 1260 91.3 80.0 92.5 71.3 27.5 0.0 410P9MNA 1480 97.5 100.0 100.0 72.5 36.3 0.0 410P9M NA 1820 96.3 100.0 100.095.0 57.5 0.0 403U7N NA 1260 96.3 100.0 100.0 87.5 32.5 0.0 403U7N NA1480 100.0 85.0 72.5 86.3 32.5 10.0 403U7N NA 1820 100.0 100.0 100.080.0 20.0 0.0 403U7N 25 1260 100.0 97.5 88.8 80.0 27.5 12.5 410P9M 75403U7N 25 1480 100.0 99.5 100.0 71.3 23.8 0.0 410P9M 75 403U7N 25 1820100.0 100.0 96.3 88.3 20.0 0.0 410P9M 75 403U7N 50 1260 88.8 97.5 100.085.0 16.3 0.0 410P9M 50 403U7N 50 1480 100.0 97.5 100.0 87.0 27.5 22.5410P9M 50 403U7N 50 1820 100.0 100.0 96.3 87.0 20.0 12.5 410P9M 50403U7N 75 1260 92.5 100.0 75.0 91.3 13.8 0.0 410P9M 25 403U7N 75 1480100.0 100.0 100.0 81.3 15.0 10.0 410P9M 25 403U7N 75 1820 100.0 100.0100.0 88.8 22.5 0.0 410P9M 25 DUAL MAGNUM NA 1400 100.0 100.0 95.0 98.877.5 25.0 DUAL MAGNUM NA 1680 100.0 100.0 100.0 100.0 50.0 17.5 DUALMAGNUM NA 1960 100.0 100.0 98.8 98.8 85.0 47.5

TABLE AMARE and SIDSP Weed Control Efficacy AMARE Product Rate 21 AMARESIDSP SIDSP Formulation Ratio g AI/ha DAT 42 DAT 21 DAT 42 DAT 410P9M NA1260 100.0 100.0 78.3 45.0 410P9M NA 1480 100.0 100.0 96.3 73.8 410P9MNA 1820 100.0 100.0 93.8 62.5 403U7N NA 1260 100.0 100.0 76.3 50.0403U7N NA 1480 100.0 100.0 78.8 52.5 403U7N NA 1820 100.0 100.0 91.381.3 403U7N 25 410P9M 75 1260 100.0 100.0 62.5 43.8 403U7N 25 410P9M 751480 100.0 100.0 88.8 61.3 403U7N 25 410P9M 75 1820 100.0 100.0 92.365.0 403U7N 50 410P9M 50 1260 100.0 100.0 66.3 28.8 403U7N 50 410P9M 501480 100.0 100.0 73.3 37.5 403U7N 50 410P9M 50 1820 100.0 100.0 90.066.3 403U7N 75 410P9M 25 1260 100.0 100.0 66.3 33.8 403U7N 75 410P9M 251480 100.0 100.0 80.0 61.3 403U7N 75 410P9M 25 1820 100.0 100.0 93.870.0 DUAL NA 1400 100.0 100.0 40.0 18.8 MAGNUM DUAL NA 1680 100.0 100.057.5 17.5 MAGNUM DUAL NA 1960 100.0 100.0 50.0 12.5 MAGNUM

TABLE ABUTH and IPOHE Weed Control Efficacy ABUTH ABUTH IPOHE IPOHEProduct Rate 21 42 21 42 Formulation Ratio g AI/ha DAT DAT DAT DAT410P9M NA 1260 8.8 7.5 18.8 7.5 410P9M NA 1480 20.0 7.5 17.5 3.8 410P9MNA 1820 21.3 8.8 25.0 7.5 403U7N NA 1260 18.8 7.5 21.3 7.5 403U7N NA1480 22.5 3.8 20.0 3.8 403U7N NA 1820 16.3 10.0 23.8 3.8 403U7N 25410P9M 75 1260 20.0 3.8 15.0 7.5 403U7N 25 410P9M 75 1480 22.5 3.8 17.510.0 403U7N 25 410P9M 75 1820 21.3 12.5 18.8 7.5 403U7N 50 410P9M 501260 11.3 13.8 7.5 7.5 403U7N 50 410P9M 50 1480 22.5 12.5 18.8 6.3403U7N 50 410P9M 50 1820 22.5 7.5 18.8 3.8 403U7N 75 410P9M 25 1260 20.03.8 21.3 10.0 75403U7N 75 410P9M 25 1480 26.3 7.5 18.8 0.0 403U7N 75410P9M 25 1820 12.5 5.0 17.5 3.8 DUAL NA 1400 16.3 5.0 11.3 8.8 MAGNUMDUAL NA 1680 20.0 7.5 10.0 5.0 MAGNUM DUAL NA 1960 18.8 6.3 33.8 3.8MAGNUM

TABLE SEBEX and DTTAE Weed Control Efficacy Product Rate SEBEX SEBEXDTTAE DTTAE Formulation Ratio g AI/ha 21 DAT 42 DAT 21 DAT 42 DAT 410P9MNA 1260 65.8 27.5 78.8 50.0 410P9M NA 1480 72.0 55.0 88.8 87.5 410P9M NA1820 80.0 60.0 100.0 100.0 403U7N NA 1260 63.3 30.0 95.0 91.3 403U7N NA1480 65.0 31.3 82.5 67.5 403U7N NA 1820 78.3 65.8 100.0 95.0 403U7N 25410P9M 75 1260 52.5 17.5 93.8 82.5 403U7N 25 410P9M 75 1480 70.8 47.591.3 85.0 403U7N 25 410P9M 75 1820 73.8 51.3 93.8 90.0 403U7N 50 410P9M50 1260 50.0 28.8 100.0 100.0 403U7N 50 410P9M 50 1480 55.0 22.5 100.097.5 403U7N 50 410P9M 50 1820 71.3 56.3 100.0 100.0 403U7N 75 410P9M 251260 38.8 17.5 95.0 92.5 403U7N 75 410P9M 25 1480 71.3 42.5 100.0 97.5403U7N 75 410P9M 25 1820 65.0 49.5 100.0 97.5 DUAL NA 1400 26.3 6.3100.0 100.0 MAGNUM DUAL NA 1680 28.8 6.3 100.0 100.0 MAGNUM DUAL NA 196038.8 12.5 100.0 100.0 MAGNUM

TABLE ELEIN and ECHCG Weed Control Efficacy Product Rate ELEIN ELEINECHCG ECHCG Formulation Ratio g AI/ha 21 DAT 42 DAT 21 DAT 42 DAT 410P9MNA 1260 100.0 100.0 72.5 32.5 410P9M NA 1480 100.0 100.0 81.3 82.5410P9M NA 1820 100.0 100.0 61.3 53.8 403U7N NA 1260 95.0 87.5 60.0 61.3403U7N NA 1480 100.0 100.0 88.8 85.0 403U7N NA 1820 100.0 100.0 81.375.0 403U7N 25 410P9M 75 1260 100.0 100.0 77.5 75.0 403U7N 25 410P9M 751480 95.0 90.0 71.3 60.0 403U7N 25 410P9M 75 1820 100.0 100.0 83.8 77.5403U7N 50 410P9M 50 1260 100.0 100.0 66.3 47.5 403U7N 50 410P9M 50 148095.0 100.0 68.8 56.3 403U7N 50 410P9M 50 1820 100.0 100.0 71.3 60.0403U7N 75 410P9M 25 1260 100.0 100.0 85.0 72.5 403U7N 75 410P9M 25 1480100.0 100.0 78.8 75.0 403U7N 75 410P9M 25 1820 100.0 100.0 78.8 71.3DUAL NA 1400 100.0 100.0 83.8 82.5 MAGNUM DUAL NA 1680 100.0 100.0 73.846.3 MAGNUM DUAL NA 1960 100.0 100.0 75.0 73.8 MAGNUM

TABLE CASOB and SEBEX Weed Control Efficacy Product Rate CASOB SEBEXFormulation Ratio g AI/ha 21 DAT 21 DAT 410P9M NA 1260 18.8 40.8 410P9MNA 1480 22.5 48.8 410P9M NA 1820 26.3 52.0 403U7N NA 1260 20.0 31.3403U7N NA 1480 28.8 30.8 403U7N NA 1820 27.5 44.5 403U7N 25 410P9M 751260 22.5 36.3 403U7N 25 410P9M 75 1480 26.3 46.3 403U7N 25 410P9M 751820 26.3 49.5 403U7N 50 410P9M 50 1260 16.3 31.3 403U7N 50 410P9M 501480 26.3 33.8 403U7N 50 410P9M 50 1820 27.5 41.3 403U7N 75 410P9M 251260 17.5 26.3 403U7N 75 410P9M 25 1480 18.8 33.8 403U7N 75 410P9M 251820 28.8 33.8 DUAL MAGNUM NA 1400 15.0 26.3 DUAL MAGNUM NA 1680 30.038.8 DUAL MAGNUM NA 1960 23.8 46.3

TABLE SIDSP and DIGSA Weed Control Efficacy Product Rate SIDSP DIGSAFormulation Ratio g AI/ha 21 DAT 21 DAT 410P9M NA 1260 67.3 100.0 410P9MNA 1480 67.0 100.0 410P9M NA 1820 77.0 100.0 403U7N NA 1260 58.8 100.0403U7N NA 1480 55.0 100.0 403U7N NA 1820 70.0 100.0 403U7N 25 410P9M 751260 61.3 100.0 403U7N 25 410P9M 75 1480 67.5 100.0 403U7N 25 410P9M 751820 71.3 100.0 403U7N 50 410P9M 50 1260 52.0 100.0 403U7N 50 410P9M 501480 61.3 100.0 403U7N 50 410P9M 50 1820 71.3 100.0 403U7N 75 410P9M 251260 56.5 95.0 403U7N 75 410P9M 25 1480 55.0 97.5 403U7N 75 410P9M 251820 66.3 99.8 DUAL MAGNUM NA 1400 47.5 100.0 DUAL MAGNUM NA 1680 61.3100.0 DUAL MAGNUM NA 1960 67.5 100.0

TABLE ABUTH and AMARE Weed Control Efficacy Product Rate ABUTH AMAREFormulation Ratio g AI/ha 21 DAT 21 DAT 410P9M NA 1260 30.0 100.0 410P9MNA 1480 35.0 100.0 410P9M NA 1820 25.0 100.0 403U7N NA 1260 23.8 100.0403U7N NA 1480 28.8 100.0 403U7N NA 1820 27.5 100.0 403U7N 25 410P9M 751260 38.8 100.0 403U7N 25 410P9M 75 1480 24.5 100.0 403U7N 25 410P9M 751820 31.3 100.0 403U7N 50 410P9M 50 1260 17.5 100.0 403U7N 50 410P9M 501480 23.8 100.0 403U7N 50 410P9M 50 1820 26.3 100.0 403U7N 75 410P9M 251260 25.0 97.5 403U7N 75 410P9M 25 1480 23.8 100.0 403U7N 75 1820 26.3100.0 410P9M 25 DUAL MAGNUM NA 1400 27.5 97.5 DUAL MAGNUM NA 1680 30.0100.0 DUAL MAGNUM NA 1960 26.3 100.0

TABLE ECHCG Weed Control Efficacy Product Rate ECHCG Formulation Ratio gAI/ha 21 DAT 410P9M NA 1260 100.0 410P9M NA 1480 100.0 410P9M NA 1820100.0 403U7N NA 1260 100.0 403U7N NA 1480 100.0 403U7N NA 1820 100.0403U7N 25 410P9M 75 1260 100.0 403U7N 25 410P9M 75 1480 100.0 403U7N 25410P9M 75 1820 100.0 403U7N 50 410P9M 50 1260 100.0 403U7N 50 410P9M 501480 100.0 403U7N 50 410P9M 50 1820 100.0 403U7N 75 410P9M 25 1260 99.8403U7N 75 410P9M 25 1480 100.0 403U7N 75 410P9M 25 1820 100.0 DUALMAGNUM NA 1400 100.0 DUAL MAGNUM NA 1680 100.0 DUAL MAGNUM NA 1960 100.0

In the above tables that show the results from Field Trial 2010530034,control of amaranthus (AMASS) was greater as application rate increasedwith each formulation evaluated. At the earliest sampling date (23 DAT),the 403U7N:410P9M encapsulated acetochlor formulation blends providedbetter control than formulations of composition 410P9M alone at thefield application rate of 1260 g ai/ha (1.125 lb ai/A). At the secondsampling date (41 DAT), both the 25:75 and 50:50 blends of 403U7N:410P9Mprovided 87.5% or better control of AMASS compared to only 55% controlwith composition 410P9M alone. Only the 25:75 blend of 403U7N:410P9Mprovided greater than 90% AMASS control at 57 DAT at field applicationrates.

Barnyardgrass (ECHCG) efficacy was similar among the variousencapsulated acetochlor formulations evaluated at all three samplingdates with 90% or greater control for 410P9M, 403U7N alone and the 50:50blend of 403U7N:410P9M nearly 2 months after application (57 DAT) atfield use rates. Signalgrass (BRAPP) efficacy was only commerciallyacceptable (>85%) for the encapsulated acetochlor formulations 403U7Nalone and the 50:50 and 75:25 blends of 403U7N:410P9M at the firstevaluation date (23 DAT).

Large seeded dicots, such as morningglory (IPOHE), sicklepod (CASOB) andvelvetleaf (ABUTH), were not controlled in this trial with theencapsulated acetochlor formulations. This is not unexpected as previousgreenhouse trials have demonstrated limited impact on these species.

In the above tables that show the results from Field Trial 2010530035,all encapsulated acetochlor formulations provided 100% control of commonamaranthus (AMARE) at both 21 and 42 DAT. At field use rates, noformulation provided acceptable prickly sida (SIDSP) control. At boththe 1480 and 1820 g ai/ha application rates, encapsulated acetochlorformulation 410P9M provided greater than 93.6% control of SIDSP for 21DAT. Only the highest application rate of 1820 g ai/ha provided 90% orgreater control of SIDSP for the various 403U7N:410P9M formulationblends at 21 DAT. No application rate or formulation provided acceptableSIDSP control at 42 DAT.

Goosegrass (ELEIN) efficacy was 100% at both 21 and 42 DAT for allencapsulated acetochlor formulations except 403U7N, which had 95 and87.5% efficacy at 21 and 42 DAT, respectively. Field use rates of allencapsulated acetochlor formulations provided 93.8% or better efficacyfor Crowfootgrass (DTTAE) except for composition 410P9M, which requiredapplication rates of 1480 g ai/ha (1.325 lb ai/A) to provide similarcontrol 21 DAT. At 42 DAT, 403U7N alone and the 50:50 and the 75:25403U7N:410P9M blends provided 91.3% or greater DTTAE efficacy.Barnyardgrass (ECHCG) efficacy was below commercially accepted levels atfield use rates for all encapsulated acetochlor formulations except the75:25 403U7N:410P9M blend at 21 DAT.

Large seeded dicots, such as morningglory (IPOHE), hemp sesbania (SEBEX)and velvetleaf (ABUTH), were not controlled in this trial with theencapsulated acetochlor formulations. This is not unexpected as previousgreenhouse trials have demonstrated limited impact on these species.

In the above tables that shows results from Field Trial 2010530036, allencapsulated acetochlor formulations provided 97.5% or greater controlof common amaranthus (AMARE) at 21 DAT. In this trial, prickly sida(SIDSP) had less than acceptable control (67.3% or less) for allencapsulated acetochlor formulations at field use application rate of1260 g ai/ha. Both crabgrass (DIGSA) and barnyardgrass (ECHCG) had 95%or better control at 21 DAT with all rates and formulations evaluated inthis trial.

Large seeded dicots, such as hemp sesbania (SEBEX), sicklepod (CASOB)and velvetleaf (ABUTH), were not controlled in this trial with theencapsulated acetochlor formulations. This is not unexpected as previousgreenhouse trials have demonstrated limited impact on these species.

Overall, weed control efficacy is equal to or better with the403U7N:410P9M encapsulated acetochlor blended formulations as comparedto composition 410P9M alone and may provide slightly longer control withsome weed species.

Example 9. Field Trial Study of Weed Control Efficacy and Soybean Safetyin Pre-Plant, At Planting, At Cracking and Early Post EmergenceApplications of Microencapsulated Acetochlor Tank Mixtures

Tank mixtures containing aqueous dispersions of microencapsulatedacetochlor formulation 410P9M prepared in Example 2 were evaluated inpre-plant (EPP), at planting (AP), at cracking (ACR) and early postemergence (EPOE) applications for crop safety in soybeans and weedcontrol efficacy.

ROUNDUP READY Soybeans were planted in four row plots with a spray areaof 2.08 m×6 m. The center two rows were utilized for crop safetyevaluations. Rows 1 and 4 were sprayed with buffer. The whole plot wasused for weed control evaluation. Unsprayed buffer between the plots oftwo rows provided a running check for weed control evaluation. Eachtreatment was run in four replicates.

The early pre-plant application (EPP) was made 14 days prior to plantingthe crop. The at cracking (ACR) application was made 5 days afterplanting. The early post-emergence application (EPOE) was made at the V1or V2 growth stage.

The crop injury ratings were taken at 21 and 42 days after treatment andwere based on the European Weed Research Scale (EWRS) as follows:

EWRS 1: injury of 0% (100% normal plants);

EWRS 2: injury of 0-2% (plants normally in a 98-100%);

EWRS 3: injury of 2-5% (plants normally in a 95-98%);

EWRS 4: injury of 5-10% (plants normally in a 90-95%);

EWRS 5: injury of 10-20%;

EWRS 6: injury of 20-40%;

EWRS 7: injury of 40-70%; and

EWRS 8: injury of 70-99%.

Weed control efficacy was evaluated at 21 and 42 days after treatment.

ROUNDUP READY soybeans were planted as described above. Tank mixturescontaining encapsulated acetochlor formulation 410P9M with ROUNDUP (Rup)were compared to DUAL MAGNUM tank mixed with ROUNDUP and ROUNDUP alone.ROUNDUP in tank mixture and alone was applied at a rate of 840 g/ha.

RR Soybean crop injury at early (21 DAT) and late (42 DAT) evaluationsfrom the combined data from 7 field trials is shown in the table below.Mean separation is within individual application and rating timings.

TABLE Appli- Product Mean Rating cation Formulation/Rate Injury Sepa-Timing Timing (g/ha) (LS Mean) SE ration Early At Plant Rup + 410P9M1960 2.3 0.2 A Early At Plant Rup + 410P9M 1680 2.2 0.2 A Early At PlantRup + 410P9M 1260 2.1 0.2 A Early At Plant Rup + DUAL MAGNUM 2.0 0.2 A1960 Early At Plant Rup + 410P9M 1120 2.0 0.2 A Early At Plant Rup +DUAL MAGNUM 1.6 0.2 B 1680 Early At Plant Rup + DUAL MAGNUM 1.5 0.2 BC1400 Early At Plant Rup + DUAL MAGNUM 1.3 0.2 BC 1120 Early At Plant Rup840 1.1 0.2 C Early Cracking Rup + 410P9M 1960 3.5 0.2 A Early CrackingRup + 410P9M 1680 3.3 0.2 AB Early Cracking Rup + 410P9M 1260 3.1 0.2 BEarly Cracking Rup + 410P9M 1120 2.7 0.2 C Early Cracking Rup + DUALMAGNUM 2.4 0.2 CD 1960 Early Cracking Rup + DUAL MAGNUM 2.2 0.2 DE 1680Early Cracking Rup + DUAL MAGNUM 2.0 0.2 EF 1400 Early Cracking Rup +DUAL MAGNUM 1.7 0.2 F 1120 Early Cracking Rup 840 1.2 0.2 G EarlyPre-Plant Rup + 410P9M 1960 2.0 0.2 A Early Pre-Plant Rup + 410P9M 12601.8 0.2 AB Early Pre-Plant Rup + 410P9M 1680 1.8 0.2 AB Early Pre-PlantRup + DUAL MAGNUM 1.6 0.2 ABC 1960 Early Pre-Plant Rup + DUAL MAGNUM 1.50.2 BCD 1680 Early Pre-Plant Rup + 410P9M 1120 1.5 0.2 BCD EarlyPre-Plant Rup + DUAL MAGNUM 1.3 0.2 CDE 1400 Early Pre-Plant Rup + DUALMAGNUM 1.2 0.2 DE 1120 Early Pre-Plant Rup 840 1.0 0.2 E Early V2 Rup +410P9M 1960 3.7 0.2 A Early V2 Rup + DUAL MAGNUM 3.4 0.2 AB 1960 EarlyV2 Rup + 410P9M 1680 3.3 0.2 BC Early V2 Rup + DUAL MAGNUM 3.2 0.2 BC1680 Early V2 Rup + 410P9M 1260 3.1 0.2 BC Early V2 Rup + DUAL MAGNUM3.0 0.2 CD 1400 Early V2 Rup + 410P9M 1120 2.7 0.2 DE Early V2 Rup +DUAL MAGNUM 2.4 0.2 E 1120 Early V2 Rup 840 1.2 0.2 F Late At PlantRup + 410P9M 1960 1.6 0.1 A Late At Plant Rup + 410P9M 1680 1.5 0.1 ALate At Plant Rup + DUAL MAGNUM 1.4 0.1 AB 1960 Late At Plant Rup +410P9M 1120 1.3 0.1 ABC Late At Plant Rup + 410P9M 1260 1.3 0.1 ABC LateAt Plant Rup + DUAL MAGNUM 1.2 0.1 BC 1120 Late At Plant Rup + DUALMAGNUM 1.2 0.1 BC 1680 Late At Plant Rup + DUAL MAGNUM 1.1 0.1 BC 1400Late At Plant Rup 840 1.0 0.1 C Late Cracking Rup + 410P9M 1960 1.9 0.1A Late Cracking Rup + 410P9M 1260 1.7 0.1 A Late Cracking Rup + 410P9M1680 1.6 0.1 AB Late Cracking Rup + DUAL MAGNUM 1.6 0.1 ABC 1960 LateCracking Rup + DUAL MAGNUM 1.4 0.1 BCD 1680 Late Cracking Rup + 410P9M1120 1.4 0.1 BCD Late Cracking Rup + DUAL MAGNUM 1.3 0.1 CD 1400 LateCracking Rup + DUAL MAGNUM 1.1 0.1 DE 1120 Late Cracking Rup 840 1.0 0.1E Late Pre-Plant Rup + 410P9M 1260 1.2 0.1 A Late Pre-Plant Rup + 410P9M1960 1.1 0.1 A Late Pre-Plant Rup + DUAL MAGNUM 1.1 0.1 A 1960 LatePre-Plant Rup + 410P9M 1680 1.1 0.1 A Late Pre-Plant Rup + DUAL MAGNUM1.0 0.1 A 1400 Late Pre-Plant Rup + DUAL MAGNUM 1.0 0.1 A 1680 LatePre-Plant Rup + 410P9M 1120 1.0 0.1 A Late Pre-Plant Rup 840 1.0 0.1 ALate Pre-Plant Rup + DUAL MAGNUM 1.0 0.1 A 1120 Late V2 Rup + 410P9M1960 2.7 0.1 A Late V2 Rup + DUAL MAGNUM 2.5 0.1 AB 1960 Late V2 Rup +410P9M 1680 2.3 0.1 BC Late V2 Rup + DUAL MAGNUM 2.2 0.1 CD 1680 Late V2Rup + 410P9M 1120 2.1 0.1 CDE Late V2 Rup + 410P9M 1260 2.1 0.1 CDE LateV2 Rup + DUAL MAGNUM 2.0 0.1 DE 1400 Late V2 Rup + DUAL MAGNUM 1.8 0.1 E1120 Late V2 Rup 840 1.1 0.1 F

Crop injury at 21 DAT with early pre-plant application ranged from 1.0(no injury) for ROUNDUP alone up to 2.0 (0-2% injury) for ROUNDUP tankmixed with the encapsulated acetochlor formulation 410P9M at 1960 gai/ha. Comparing the current field application rates of 410P9M (1260 gai/ha) to DUAL MAGNUM (1400 g ai/ha), the encapsulated acetochlorformulation 410P9M had significantly greater injury level than DUALMAGNUM (1.8 (0-2% injury) versus 1.3 (0-1% injury)). However, this isnot a level of injury that would be noticeable in the field withoutuntreated controls present. By the late evaluation date (42 DAT), therewas no significant difference in crop injury with any of the treatments.

Crop injury at 21 DAT with at planting application ranged from 1.1 (noinjury) for ROUNDUP alone to 2.3 (2% injury) for ROUNDUP tank mixed withthe encapsulated acetochlor formulation 410P9M at 1960 g ai/ha. Thelevel of injury with composition 410P9M at 1260 g ai/ha wassignificantly greater than found on plants treated with DUAL MAGNUM at1400 g ai/ha, 2.1 (2% injury) compared to 1.5 (1% injury). While thesedifferences are statistically different they would not be noticeableunder field conditions without untreated controls present. By the lateevaluation (42 DAT), foliar injury levels were 1.6 or less (<2% injury)for all treatments with field use rates of the encapsulated acetochlorformulation 410P9M and DUAL MAGNUM having similar levels of injury.

For the at cracking application timing, the injury level for theencapsulated acetochlor formulation 410P9M was greater than DUAL MAGNUMat all application rates. Crop injury at 21 DAT with at crackingapplication ranged from 1.2 (no injury) for ROUNDUP alone to 3.5 (2-5%injury) for ROUNDUP tank mixed with composition 410P9M at 1960 g ai/ha.The level of injury with composition 410P9M at 1260 g ai/ha wassignificantly greater than found on plants treated with DUAL MAGNUM at1400 g ai/ha, 3.1 (2-5% injury) compared to 2.0 (0-2% injury). Thesedifferences between treatments may be noticeable, but would still beconsidered minor and not a threat to crop yield. At 42 DAT, all injuryratings were 1.9 or less (0-2% injury) for all treatments. Field userates of the encapsulated acetochlor formulation 410P9M (1260 g ai/ha)were significantly greater than that of DUAL MAGNUM (1400 g ai/ha), 1.7(0-2% injury) versus 0.3(0-1% injury).

For the early post application timing, the injury level of theencapsulated acetochlor formulation 410P9M was similar to DUAL MAGNUMwithin each application rate. Crop injury at 21 DAT with an early postapplication ranged from 1.2 (no injury) for ROUNDUP alone to 3.7 (5%injury) for ROUNDUP tank mixed with the encapsulated acetochlorformulation 410P9M at 1960 g ai/ha. The level of injury with composition410P9M at 1260 g ai/ha was similar to that found on plants treated withDUAL MAGNUM at 1400 g ai/ha, 3.1 versus 3.0 (2-5% injury). At the 42 DATevaluation, both the encapsulated acetochlor formulation 410P9M and DUALMAGNUM at field use rates had similar levels of crop injury of 2.0-2.1(0-2% injury).

No crop injury was observed for the early pre-plant or at plantingapplication of the herbicides at the six trial locations. For the atcracking applications, injury was observed at one trial location at 21DAT. No significant differences in crop injury were observed with thisapplication timing based on treatment or rate. Injury was minor with 5%or less reported at this trial location. No injury was reported at 42DAT.

Three trial locations reported injury with the early post applicationtiming at 21 DAT. At two locations, DUAL MAGNUM applications causedsignificantly greater injury than formulations of composition 410P9M atfield use rates. DUAL MAGNUM (1400 g ai/ha) caused between 8.1-12.5%injury, while the encapsulated acetochlor formulation 410P9M (1260 gai/ha) had no injury observed. In the third trial, composition 410P9M(1260 g ai/ha) had 6.0% injury, while no injury was noted with DUALMAGNUM (1400 g ai/ha). These levels of injury are not considered highenough to cause reductions in crop yield with RR Soybeans.

Weed efficacy on crabgrass (DIGSA), purslane (POROL), and quitensisamaranthus (AMAQU) at early (21 DAT) and late (42 DAT) evaluations fromthe combined data from 7 field trials is shown in the table below. Meanseparation is within individual application and rating timings.

TABLE Product Weed Weed Application Formulation/ Control Mean SpeciesDAT Timing Rate (g/ha) (LS Mean) SE Separation DIGSA 21 At Plant Rup +DUAL 92 3.9 A MAGNUM 1680 DIGSA 21 At Plant Rup + 410P9M 90 3.9 AB 1960DIGSA 21 At Plant Rup + DUAL 90 3.9 AB MAGNUM 1960 DIGSA 21 At PlantRup + DUAL 89 3.9 AB MAGNUM 1400 DIGSA 21 At Plant Rup + DUAL 89 3.9 ABCMAGNUM 1120 DIGSA 21 At Plant Rup + 410P9M 87 3.9 BC 1680 DIGSA 21 AtPlant Rup + 410P9M 86 3.9 C 1260 DIGSA 21 At Plant Rup + 410P9M 85 3.9CD 1120 DIGSA 21 At Plant Rup 840 82 3.9 D DIGSA 21 Cracking Rup + DUAL97 3.0 A MAGNUM 1960 DIGSA 21 Cracking Rup + 410P9M 97 3.0 A 1680 DIGSA21 Cracking Rup + 410P9M 96 3.0 A 1960 DIGSA 21 Cracking Rup + 410P9M 963.0 A 1120 DIGSA 21 Cracking Rup + 410P9M 95 3.0 AB 1260 DIGSA 21Cracking Rup + DUAL 94 3.0 ABC MAGNUM 1680 DIGSA 21 Cracking Rup + DUAL91 3.0 BCD MAGNUM 1400 DIGSA 21 Cracking Rup 840 90 3.0 CD DIGSA 21Cracking Rup + DUAL 89 3.0 D MAGNUM 1120 DIGSA 21 Pre-Plant Rup + 410P9M82 8.4 A 1960 DIGSA 21 Pre-Plant Rup + DUAL 78 8.4 AB MAGNUM 1960 DIGSA21 Pre-Plant Rup + 410P9M 73 8.4 ABC 1680 DIGSA 21 Pre-Plant Rup + DUAL72 8.4 BC MAGNUM 1680 DIGSA 21 Pre-Plant Rup + 410P9M 70 8.4 BC 1260DIGSA 21 Pre-Plant Rup + DUAL 70 8.4 BC MAGNUM 1400 DIGSA 21 Pre-PlantRup + 410P9M 67 8.4 C 1120 DIGSA 21 Pre-Plant Rup + DUAL 66 8.4 C MAGNUM1120 DIGSA 21 Pre-Plant Rup 840 43 8.4 D DIGSA 21 V2 Rup + DUAL 99 1.1 AMAGNUM 1960 DIGSA 21 V2 Rup + DUAL 98 1.1 AB MAGNUM 1400 DIGSA 21 V2Rup + DUAL 98 1.1 AB MAGNUM 1680 DIGSA 21 V2 Rup + 410P9M 98 1.1 AB 1680DIGSA 21 V2 Rup + 410P9M 97 1.1 AB 1260 DIGSA 21 V2 Rup + 410P9M 97 1.1AB 1960 DIGSA 21 V2 Rup + DUAL 97 1.1 B MAGNUM 1120 DIGSA 21 V2 Rup +410P9M 97 1.1 B 1120 DIGSA 21 V2 Rup 840 95 1.1 C DIGSA 42 At PlantRup + DUAL 76 7.7 A MAGNUM 1680 DIGSA 42 At Plant Rup + 410P9M 74 7.7 AB1960 DIGSA 42 At Plant Rup + DUAL 74 7.7 AB MAGNUM 1960 DIGSA 42 AtPlant Rup + 410P9M 69 7.7 ABC 1680 DIGSA 42 At Plant Rup + 410P9M 68 7.7BC 1260 DIGSA 42 At Plant Rup + 410P9M 66 7.7 C 1120 DIGSA 42 At PlantRup + DUAL 66 7.7 C MAGNUM 1400 DIGSA 42 At Plant Rup + DUAL 64 7.7 CMAGNUM 1120 DIGSA 42 At Plant Rup 840 49 7.7 D DIGSA 42 Cracking Rup +410P9M 92 5.6 A 1680 DIGSA 42 Cracking Rup + 410P9M 89 5.6 AB 1960 DIGSA42 Cracking Rup + DUAL 89 5.6 AB MAGNUM1960 DIGSA 42 Cracking Rup + DUAL85 5.6 AB MAGNUM 1400 DIGSA 42 Cracking Rup + 410P9M 85 5.6 AB 1260DIGSA 42 Cracking Rup + DUAL 83 5.6 B MAGNUM 1680 DIGSA 42 CrackingRup + 410P9M 82 5.6 B 1120 DIGSA 42 Cracking Rup + DUAL 72 5.6 C MAGNUM1120 DIGSA 42 Cracking Rup 840 68 5.6 C DIGSA 42 Pre-Plant Rup + 410P9M62 8.5 A 1680 DIGSA 42 Pre-Plant Rup + DUAL 59 8.5 AB MAGNUM 1960 DIGSA42 Pre-Plant Rup + 410P9M 58 8.5 AB 1960 DIGSA 42 Pre-Plant Rup + 410P9M55 8.5 BC 1260 DIGSA 42 Pre-Plant Rup + DUAL 54 8.5 BC MAGNUM 1680 DIGSA42 Pre-Plant Rup + DUAL 54 8.5 BC MAGNUM 1400 DIGSA 42 Pre-Plant Rup +410P9M 50 8.5 C 1120 DIGSA 42 Pre-Plant Rup + DUAL 48 8.5 C MAGNUM 1120DIGSA 42 Pre-Plant Rup 840 25 8.5 D DIGSA 42 V2 Rup + DUAL 96 2.6 AMAGNUM 1400 DIGSA 42 V2 Rup + DUAL 95 2.6 AB MAGNUM 1960 DIGSA 42 V2Rup + DUAL 94 2.6 ABC MAGNUM 1680 DIGSA 42 V2 Rup + DUAL 92 2.6 ABCDMAGNUM 1120 DIGSA 42 V2 Rup + 410P9M 92 2.6 ABCD 1960 DIGSA 42 V2 Rup +410P9M 90 2.6 BCD 1680 DIGSA 42 V2 Rup + 410P9M 89 2.6 CD 1120 DIGSA 42V2 Rup + 410P9M 88 2.6 D 1260 DIGSA 42 V2 Rup 840 83 2.6 E POROL 21 AtPlant Rup + 410P9M 84 8.8 A 1960 POROL 21 At Plant Rup + 410P9M 82 8.8 A1680 POROL 21 At Plant Rup + 410P9M 79 8.8 A 1120 POROL 21 At PlantRup + 410P9M 79 8.8 A 1260 POROL 21 At Plant Rup + DUAL 78 8.8 A MAGNUM1960 POROL 21 At Plant Rup + DUAL 77 8.8 A MAGNUM 1400 POROL 21 At PlantRup + DUAL 75 8.8 A MAGNUM 1120 POROL 21 At Plant Rup840 75 8.8 A POROL21 At Plant Rup + DUAL 74 8.8 A MAGNUM 1680 POROL 21 Cracking Rup +410P9M 92 6.7 A 1680 POROL 21 Cracking Rup + DUAL 91 6.7 A MAGNUM 1960POROL 21 Cracking Rup + DUAL 87 6.7 A MAGNUM 1120 POROL 21 CrackingRup + 410P9M 87 6.7 A 1260 POROL 21 Cracking Rup + 410P9M 87 6.7 A 1960POROL 21 Cracking Rup + DUAL 86 6.7 A MAGNUM1400 POROL 21 Cracking Rup +DUAL 85 6.7 A MAGNUM 1680 POROL 21 Cracking Rup + 410P9M 83 6.7 A 1120POROL 21 Cracking Rup 840 81 6.7 A POROL 21 Pre-Plant Rup + 410P9M 7413.5 A 1960 POROL 21 Pre-Plant Rup + DUAL 70 13.5 AB MAGNUM 1400 POROL21 Pre-Plant Rup + 410P9M 67 13.5 AB 1680 POROL 21 Pre-Plant Rup +410P9M 65 13.5 AB 1260 POROL 21 Pre-Plant Rup + 410P9M 65 13.5 AB 1120POROL 21 Pre-Plant Rup + DUAL 64 13.5 AB MAGNUM 1960 POROL 21 Pre-PlantRup + DUAL 58 13.5 ABC MAGNUM 1680 POROL 21 Pre-Plant Rup + DUAL 57 13.5BC MAGNUM 1120 POROL 21 Pre-Plant Rup 840 43 13.5 C POROL 21 V2 Rup +DUAL 92 6.4 A MAGNUM 1960 POROL 21 V2 Rup + 410P9M 91 6.4 A 1960 POROL21 V2 Rup + DUAL 91 6.4 A MAGNUM 1120 POROL 21 V2 Rup + DUAL 90 6.4 AMAGNUM 1680 POROL 21 V2 Rup 840 90 6.4 A POROL 21 V2 Rup + 410P9M 88 6.4A 1680 POROL 21 V2 Rup + 410P9M 88 6.4 A 1260 POROL 21 V2 Rup + DUAL 886.4 A MAGNUM 1400 POROL 21 V2 Rup + 410P9M 86 6.4 A 1120 POROL 42 AtPlant Rup + 410P9M 65 22.7 A 1960 POROL 42 At Plant Rup + 410P9M 60 22.7A 1680 POROL 42 At Plant Rup + DUAL 57 22.7 A MAGNUM 1680 POROL 42 AtPlant Rup 840 56 22.7 A POROL 42 At Plant Rup + DUAL 56 22.7 A MAGNUM400 POROL 42 At Plant Rup + DUAL 56 22.7 A MAGNUM 960 POROL 42 At PlantRup + 410P9M 56 22.7 A 1260 POROL 42 At Plant Rup + DUAL 53 22.7 AMAGNUM 1120 POROL 42 At Plant Rup + 410P9M 52 22.7 A 1120 POROL 42Cracking Rup + 410P9M 79 19.0 A 1680 POROL 42 Cracking Rup + 410P9M 7019.0 AB 1260 POROL 42 Cracking Rup + 410P9M 69 19.0 AB 1960 POROL 42Cracking Rup + 410P9M 66 19.0 B 1120 POROL 42 Cracking Rup + DUAL 6119.0 BC MAGNUM 1680 POROL 42 Cracking Rup + DUAL 61 19.0 BC MAGNUM 1400POROL 42 Cracking Rup + DUAL 60 19.0 BC MAGNUM 1120 POROL 42 CrackingRup + DUAL 58 19.0 BC MAGNUM 1960 POROL 42 Cracking Rup 840 53 19.0 CPOROL 42 Pre-Plant Rup + 410P9M 65 22.6 A 1960 POROL 42 Pre-Plant Rup +410P9M 57 22.6 AB 1120 POROL 42 Pre-Plant Rup + 410P9M 54 22.6 ABC 1260POROL 42 Pre-Plant Rup + 410P9M 47 22.6 BC 1680 POROL 42 Pre-Plant Rup +DUAL 43 22.6 BCD MAGNUM 1400 POROL 42 Pre-Plant Rup + DUAL 43 22.6 BCDMAGNUM 1960 POROL 42 Pre-Plant Rup + DUAL 40 22.6 CD MAGNUM 1120 POROL42 Pre-Plant Rup + DUAL 39 22.6 CD MAGNUM 1680 POROL 42 Pre-Plant Rup840 28 22.6 D POROL 42 V2 Rup + DUAL 91 11.4 A MAGNUM 1680 POROL 42 V2Rup + DUAL 90 11.4 A MAGNUM 1960 POROL 42 V2 Rup + DUAL 84 11.4 ABMAGNUM 1120 POROL 42 V2 Rup + DUAL 81 11.4 ABC MAGNUM 1400 POROL 42 V2Rup + 410P9M 80 11.4 ABC 1960 POROL 42 V2 Rup + 410P9M 78 11.4 BC 1680POROL 42 V2 Rup 840 78 11.4 BC POROL 42 V2 Rup + 410P9M 73 11.4 C 1260POROL 42 V2 Rup + 410P9M 73 11.4 C 1120 AMAQU 21 At Plant Rup + DUAL 1000.2 A MAGNUM 1680 AMAQU 21 At Plant Rup + 410P9M 100 0.2 A 1260 AMAQU 21At Plant Rup + 410P9M 100 0.2 A 1680 AMAQU 21 At Plant Rup + 410P9M 1000.2 A 1960 AMAQU 21 At Plant Rup + DUAL 100 0.2 A MAGNUM 1120 AMAQU 21At Plant Rup + DUAL 100 0.2 A MAGNUM 1400 AMAQU 21 At Plant Rup + DUAL100 0.2 A MAGNUM 1960 AMAQU 21 At Plant Rup + 410P9M 100 0.2 A 1120AMAQU 21 At Plant Rup 840 98 0.2 B AMAQU 21 Cracking Rup + DUAL 100 1.1A MAGNUM 1400 AMAQU 21 Cracking Rup + DUAL 100 1.1 A MAGNUM 1960 AMAQU21 Cracking Rup + 410P9M 100 1.1 A 1680 AMAQU 21 Cracking Rup + 410P9M100 1.1 A 1960 AMAQU 21 Cracking Rup + 410P9M 99 1.1 AB 1120 AMAQU 21Cracking Rup + DUAL 99 1.1 AB MAGNUM 1120 AMAQU 21 Cracking Rup + DUAL99 1.1 AB MAGNUM 1680 AMAQU 21 Cracking Rup + 410P9M 99 1.1 AB 1260AMAQU 21 Cracking Rup 840 97 1.1 B AMAQU 21 Pre-Plant Rup + 410P9M 991.8 A 1960 AMAQU 21 Pre-Plant Rup + 410P9M 99 1.8 AB 1680 AMAQU 21Pre-Plant Rup + 410P9M 98 1.8 AB 1260 AMAQU 21 Pre-Plant Rup + DUAL 981.8 AB MAGNUM 1680 AMAQU 21 Pre-Plant Rup + DUAL 98 1.8 AB MAGNUM 1960AMAQU 21 Pre-Plant Rup + 410P9M 98 1.8 AB 1120 AMAQU 21 Pre-Plant Rup +DUAL 97 1.8 AB MAGNUM 1400 AMAQU 21 Pre-Plant Rup + DUAL 95 1.8 B MAGNUM1120 AMAQU 21 Pre-Plant Rup 840 88 1.8 C AMAQU 42 At Plant Rup + 410P9M100 14.1 A 1120 AMAQU 42 At Plant Rup + DUAL 78 14.1 AB MAGNUM 1680AMAQU 42 At Plant Rup + 410P9M 78 14.1 AB 1680 AMAQU 42 At Plant Rup +DUAL 70 14.1 AB MAGNUM 1120 AMAQU 42 At Plant Rup 840 67 14.1 AB AMAQU42 At Plant Rup + 410P9M 64 14.1 B 1260 AMAQU 42 At Plant Rup + DUAL 6314.1 B MAGNUM 1400 AMAQU 42 At Plant Rup + DUAL 63 14.1 B MAGNUM 1960AMAQU 42 At Plant Rup + 410P9M 58 14.1 B 1960 AMAQU 42 Cracking Rup +DUAL 89 16.8 A MAGNUM 1120 AMAQU 42 Cracking Rup + DUAL 81 16.8 A MAGNUM1400 AMAQU 42 Cracking Rup + 410P9M 80 16.8 A 1960 AMAQU 42 CrackingRup + 410P9M 79 16.8 A 1260 AMAQU 42 Cracking Rup + 410P9M 79 16.8 A1680 AMAQU 42 Cracking Rup + 410P9M 74 16.8 A 1120 AMAQU 42 CrackingRup + DUAL 71 16.8 A MAGNUM 1960 AMAQU 42 Cracking Rup + DUAL 66 16.8 AMAGNUM 1680 AMAQU 42 Cracking Rup 840 59 16.8 A AMAQU 42 Pre-Plant Rup +DUAL 98 14.0 A MAGNUM 1680 AMAQU 42 Pre-Plant Rup + 410P9M 98 14.0 A1260 AMAQU 42 Pre-Plant Rup + DUAL 80 14.0 A MAGNUM1400 AMAQU 42Pre-Plant Rup + 410P9M 78 14.0 A 1120 AMAQU 42 Pre-Plant Rup + DUAL 7014.0 A MAGNUM 1120 AMAQU 42 Pre-Plant Rup + 410P9M 68 14.0 A 1960 AMAQU42 Pre-Plant Rup + DUAL 65 14.0 A MAGNUM 960 AMAQU 42 Pre-Plant Rup 84065 14.0 A AMAQU 42 Pre-Plant Rup + 410P9M 60 14.0 A 1680 AMAQU 42 V2Rup + 410P9M 100 9.7 A 1680 AMAQU 42 V2 Rup + 410P9M 100 9.7 A 1960AMAQU 42 V2 Rup + DUAL 93 9.7 A MAGNUM 1120 AMAQU 42 V2 Rup + DUAL 899.7 A MAGNUM 1960 AMAQU 42 V2 Rup + 410P9M 89 9.7 A 1260 AMAQU 42 V2Rup + DUAL 83 9.7 A MAGNUM 1400 AMAQU 42 V2 Rup 840 79 9.7 A AMAQU 42 V2Rup + DUAL 71 9.7 A MAGNUM 1680 AMAQU 42 V2 Rup + 410P9M 71 9.7 A 1120

In this study, Crabgrass (DIGSA) efficacy was similar for field userates of the encapsulated acetochlor formulation 410P9M (1260 g ai/ha)and DUAL MAGNUM (1400 g ai/ha) for the early pre-plant, at cracking andearly post applications. With the at planting application, DUAL MAGNUMwas more efficacious than the encapsulated acetochlor formulation 410P9M(89% versus 86%) at 21 DAT. Both the at cracking and early postapplications provided greater than 90% DIGSA efficacy 21 DAT.

At the second sampling date, 42 DAT, DIGSA efficacy was similar forfield use rates of the encapsulated acetochlor formulation 410P9M andDUAL MAGNUM for the early pre-plant, at planting and at crackingapplication. With the early post application, DUAL MAGNUM providedsignificantly greater DIGSA control than the encapsulated acetochlorformulation 410P9M (96% versus 88%).

Common purslane (POROL) efficacy was similar for both formulations ofthe encapsulated acetochlor formulation 410P9M and DUAL MAGNUM at allapplication timings with field application rates at 21 DAT. At-crackingapplications provided 87% control and early post application provided88% control of POROL. At 42 DAT, no application timing providedcommercially acceptable POROL control with field use rates of theseherbicides.

Quitensis amaranthus (AMAQU) efficacy was similar for field use rates ofthe encapsulated acetochlor formulation 410P9M and DUAL MAGNUM for theearly pre-plant, at planting and at cracking applications with greaterthan 97% control at 21 DAT. No data was taken for the 21 DAT rating forthe early post applications. At 42 DAT, efficacy was statistically thesame for field use rates of the encapsulated acetochlor formulation410P9M and DUAL MAGNUM, but only composition 410P9M provided acceptableAMAQU control with the early pre-plant and early post applications.

Weed efficacy on smooth pigweed (AMACH), lambsquarters (CHEAL), datura(DATFE), and wild marigold (TAGMI) at early (21 DAT) and late (42 DAT)evaluations from the combined data from 6 field trials is shown in thetable below. Mean separation is within individual application and ratingtimings.

TABLE Product Weed Application Formulation/ % Efficacy Mean Species DATTiming Rate (g/ha) (LS Mean) SE Separation AMACH 21 At Plant Rup + DUAL100.0 3.74 A MAGNUM 1400 AMACH 21 At Plant Rup + DUAL 100.0 3.74 AMAGNUM 1680 AMACH 21 At Plant Rup + DUAL 100.0 3.74 A MAGNUM 1960 AMACH21 At Plant Rup + 410P9M 99.5 3.74 A 1680 AMACH 21 At Plant Rup + 410P9M98.8 3.74 A 1960 AMACH 21 At Plant Rup + 410P9M 98.3 4.32 A 1260 AMACH21 At Plant Rup + DUAL 96.3 3.74 A MAGNUM 1120 AMACH 21 At Plant Rup +410P9M 77.5 3.74 B 1120 AMACH 21 At Plant Rup 840 62.5 3.74 C AMACH 21Cracking Rup + 410P9M 99.0 4.82 A 1260 AMACH 21 Cracking Rup + 410P9M98.8 4.75 A 1120 AMACH 21 Cracking Rup + 410P9M 98.8 4.75 A 1960 AMACH21 Cracking Rup + 410P9M 97.3 4.75 A 1680 AMACH 21 Cracking Rup + DUAL96.8 4.82 A MAGNUM 1960 AMACH 21 Cracking Rup + DUAL 95.3 5.23 A MAGNUM1680 AMACH 21 Cracking Rup + DUAL 91.6 4.75 A MAGNUM 1400 AMACH 21Cracking Rup + DUAL 87.0 4.82 A MAGNUM 1120 AMACH 21 Cracking Rup 84085.6 4.82 A AMACH 21 Pre-Plant Rup + DUAL 100.0 1.50 A MAGNUM 1680 AMACH21 Pre-Plant Rup + DUAL 100.0 1.50 A MAGNUM 1960 AMACH 21 Pre-PlantRup + 410P9M 100.0 1.50 A 1120 AMACH 21 Pre-Plant Rup 840 100.0 1.50 AAMACH 21 Pre-Plant Rup + DUAL 99.4 1.50 A MAGNUM 1400 AMACH 21 Pre-PlantRup + 410P9M 99.4 1.50 A 1680 AMACH 21 Pre-Plant Rup + 410P9M 99.4 1.50A 1960 AMACH 21 Pre-Plant Rup + 410P9M 97.5 1.50 A 1260 AMACH 21Pre-Plant Rup + DUAL 96.6 1.50 A MAGNUM 1120 AMACH 21 V2 Rup + DUAL100.0 2.55 A MAGNUM 1400 AMACH 21 V2 Rup + 410P9M 99.9 2.61 A 1960 AMACH21 V2 Rup + 410P9M 98.8 2.57 A 1120 AMACH 21 V2 Rup + DUAL 98.7 2.55 AMAGNUM1680 AMACH 21 V2 Rup + DUAL 98.6 2.57 A MAGNUM 1120 AMACH 21 V2Rup + DUAL 97.9 2.57 A MAGNUM 1960 AMACH 21 V2 Rup + 410P9M 97.5 2.57 A1680 AMACH 21 V2 Rup + 410P9M 97.2 2.55 A 1260 AMACH 21 V2 Rup 840 93.42.55 A AMACH 42 At Plant Rup + DUAL 99.4 10.56 A MAGNUM 1960 AMACH 42 AtPlant Rup + 410P9M 96.2 10.56 A 1680 AMACH 42 At Plant Rup + DUAL 95.010.56 A MAGNUM 1680 AMACH 42 At Plant Rup + DUAL 94.4 10.56 A MAGNUM1400 AMACH 42 At Plant Rup + 410P9M 89.6 10.66 A 1960 AMACH 42 At PlantRup + DUAL 89.4 10.56 A MAGNUM 1120 AMACH 42 At Plant Rup + 410P9M 88.710.56 A 1260 AMACH 42 At Plant Rup + 410P9M 71.9 10.56 A 1120 AMACH 42At Plant Rup 840 59.7 10.66 A AMACH 42 Cracking Rup + DUAL 95.7 8.28 AMAGNUM 1680 AMACH 42 Cracking Rup + DUAL 93.8 8.11 A MAGNUM 1960 AMACH42 Cracking Rup + 410P9M 91.3 8.11 AB 1680 AMACH 42 Cracking Rup +410P9M 91.0 8.11 AB 1960 AMACH 42 Cracking Rup + 410P9M 90.6 8.11 AB1260 AMACH 42 Cracking Rup + 410P9M 89.2 8.28 AB 1120 AMACH 42 CrackingRup + DUAL 81.3 8.11 B MAGNUM 1400 AMACH 42 Cracking Rup 840 66.2 8.28 CAMACH 42 Cracking Rup + DUAL 63.9 8.51 C MAGNUM 1120 AMACH 42 Pre-PlantRup + 410P9M 91.2 12.86 A 1960 AMACH 42 Pre-Plant Rup + DUAL 91.2 12.86A MAGNUM 1960 AMACH 42 Pre-Plant Rup + 410P9M 88.1 12.86 A 1680 AMACH 42Pre-Plant Rup + 410P9M 87.2 12.86 A 1120 AMACH 42 Pre-Plant Rup + DUAL85.0 12.86 A MAGNUM 1400 AMACH 42 Pre-Plant Rup + DUAL 84.4 12.86 AMAGNUM 1680 AMACH 42 Pre-Plant Rup + 410P9M 82.2 12.86 A 1260 AMACH 42Pre-Plant Rup + DUAL 81.6 12.86 A MAGNUM 1120 AMACH 42 Pre-Plant Rup 84077.2 12.86 A AMACH 42 V2 Rup + 410P9M 100.0 2.35 A 1960 AMACH 42 V2Rup + DUAL 100.0 2.20 A MAGNUM 1400 AMACH 42 V2 Rup + 410P9M 98.8 2.20AB 1260 AMACH 42 V2 Rup + DUAL 98.8 2.20 AB MAGNUM 1680 AMACH 42 V2Rup + 410P9M 97.9 2.35 AB 1120 AMACH 42 V2 Rup + DUAL 97.4 2.35 ABMAGNUM 960 AMACH 42 V2 Rup + DUAL 96.6 2.35 AB MAGNUM 1120 AMACH 42 V2Rup + 410P9M 93.3 2.35 BC 1680 AMACH 42 V2 Rup 840 87.5 2.20 C CHEAL 21At Plant Rup + DUAL 81.6 16.62 A MAGNUM 960 CHEAL 21 At Plant Rup + DUAL80.2 16.78 A MAGNUM 1680 CHEAL 21 At Plant Rup + DUAL 75.7 16.53 AMAGNUM 1400 CHEAL 21 At Plant Rup + 410P9M 75.0 16.53 A 1960 CHEAL 21 AtPlant Rup + 410P9M 74.9 16.62 A 1260 CHEAL 21 At Plant Rup + DUAL 73.516.53 A MAGNUM 1120 CHEAL 21 At Plant Rup + 410P9M 73.4 16.62 A 1680CHEAL 21 At Plant Rup + 410P9M 72.5 16.62 A 1120 CHEAL 21 At Plant Rup840 41.6 16.62 A CHEAL 21 Cracking Rup + DUAL 98.8 3.63 A MAGNUM 1680CHEAL 21 Cracking Rup + 410P9M 96.4 3.63 A 1120 CHEAL 21 Cracking Rup +DUAL 95.8 3.63 A MAGNUM 1120 CHEAL 21 Cracking Rup + 410P9M 95.5 3.63 A1260 CHEAL 21 Cracking Rup + 410P9M 94.8 3.63 A 1680 CHEAL 21 CrackingRup + 410P9M 93.9 3.63 A 1960 CHEAL 21 Cracking Rup + DUAL 93.6 3.63 AMAGNUM 1400 CHEAL 21 Cracking Rup + DUAL 93.1 3.63 A MAGNUM 1960 CHEAL21 Cracking Rup 840 90.9 3.63 A CHEAL 42 At Plant Rup + DUAL 76.7 14.78A MAGNUM 1960 CHEAL 42 At Plant Rup + DUAL 56.9 14.78 A MAGNUM 1680CHEAL 42 At Plant Rup + DUAL 56.3 14.78 A MAGNUM 1400 CHEAL 42 At PlantRup + DUAL 48.1 14.78 A MAGNUM 1120 CHEAL 42 At Plant Rup + 410P9M 46.314.78 A 1120 CHEAL 42 At Plant Rup + 410P9M 35.6 14.78 A 1960 CHEAL 42At Plant Rup + 410P9M 35.6 14.78 A 1680 CHEAL 42 At Plant Rup + 410P9M26.9 14.78 A 1260 CHEAL 42 At Plant Rup 840 17.5 14.78 A CHEAL 42Cracking Rup + DUAL 91.3 10.75 A MAGNUM 1680 CHEAL 42 Cracking Rup +DUAL 86.3 10.75 A MAGNUM 1120 CHEAL 42 Cracking Rup + 410P9M 85.9 10.75A 1260 CHEAL 42 Cracking Rup + 410P9M 85.6 10.75 A 1680 CHEAL 42Cracking Rup + DUAL 85.4 10.75 A MAGNUM 1400 CHEAL 42 Cracking Rup +DUAL 79.6 10.75 A MAGNUM 1960 CHEAL 42 Cracking Rup + 410P9M 79.4 10.75A 1120 CHEAL 42 Cracking Rup + 410P9M 76.9 10.75 A 1960 CHEAL 42Cracking Rup 840 62.5 10.75 A DATFE 21 At Plant Rup + DUAL 97.7 5.97 AMAGNUM 1680 DATFE 21 At Plant Rup + DUAL 97.2 5.97 A MAGNUM 1960 DATFE21 At Plant Rup + DUAL 96.7 5.97 A MAGNUM 1120 DATFE 21 At Plant Rup +DUAL 95.1 5.97 A MAGNUM 1400 DATFE 21 At Plant Rup + 410P9M 95.0 5.97 A1960 DATFE 21 At Plant Rup + 410P9M 94.2 5.97 A 1680 DATFE 21 At PlantRup + 410P9M 92.5 5.97 A 1120 DATFE 21 At Plant Rup + 410P9M 90.2 5.97 A1260 DATFE 21 At Plant Rup 840 89.0 5.97 A DATFE 21 Cracking Rup + DUAL97.9 1.86 A MAGNUM 1680 DATFE 21 Cracking Rup + DUAL 96.8 1.86 A MAGNUM1960 DATFE 21 Cracking Rup + 410P9M 96.0 1.86 A 1680 DATFE 21 CrackingRup + DUAL 95.9 1.86 A MAGNUM 1120 DATFE 21 Cracking Rup + 410P9M 95.31.86 A 1120 DATFE 21 Cracking Rup + DUAL 95.1 1.86 A MAGNUM 1400 DATFE21 Cracking Rup + 410P9M 94.6 1.86 A 1260 DATFE 21 Cracking Rup + 410P9M94.1 1.86 A 1960 DATFE 21 Cracking Rup 840 87.6 1.86 A DATFE 21Pre-Plant Rup + 410P9M 99.5 1.11 A 1680 DATFE 21 Pre-Plant Rup + DUAL99.1 1.11 A MAGNUM 1960 DATFE 21 Pre-Plant Rup + DUAL 99.0 1.11 A MAGNUM1680 DATFE 21 Pre-Plant Rup + 410P9M 99.0 1.11 A 1960 DATFE 21 Pre-PlantRup 840 98.9 1.11 A DATFE 21 Pre-Plant Rup + 410P9M 98.7 1.11 A 1120DATFE 21 Pre-Plant Rup + DUAL 98.6 1.11 A MAGNUM 1400 DATFE 21 Pre-PlantRup + 410P9M 98.4 1.11 A 1260 DATFE 21 Pre-Plant Rup + DUAL 97.6 1.11 AMAGNUM 1120 DATFE 21 V2 Rup + DUAL 98.8 2.33 A MAGNUM 1400 DATFE 21 V2Rup + DUAL 98.8 2.33 A MAGNUM 1960 DATFE 21 V2 Rup + 410P9M 98.5 2.33 A1260 DATFE 21 V2 Rup + 410P9M 98.5 2.33 A 1680 DATFE 21 V2 Rup + DUAL98.1 2.38 A MAGNUM 1120 DATFE 21 V2 Rup + 410P9M 98.1 2.33 A 1960 DATFE21 V2 Rup + DUAL 97.8 2.33 A MAGNUM 1680 DATFE 21 V2 Rup + 410P9M 97.52.33 A 1120 DATFE 21 V2 Rup 840 95.4 2.33 A DATFE 42 Cracking Rup +410P9M 95.6 8.05 A 1680 DATFE 42 Cracking Rup + DUAL 95.1 8.05 A MAGNUM1400 DATFE 42 Cracking Rup + DUAL 95.0 8.05 A MAGNUM 1960 DATFE 42Cracking Rup + 410P9M 94.4 8.05 A 1960 DATFE 42 Cracking Rup + DUAL 93.98.05 A MAGNUM 1680 DATFE 42 Cracking Rup + DUAL 92.7 8.05 A MAGNUM 1120DATFE 42 Cracking Rup + 410P9M 91.9 8.05 A 1260 DATFE 42 Cracking Rup +410P9M 91.2 8.05 A 1120 DATFE 42 Cracking Rup 840 77.1 8.05 A DATFE 42Pre-Plant Rup + DUAL 93.2 5.18 A MAGNUM 1960 DATFE 42 Pre-Plant Rup +DUAL 91.6 5.18 A MAGNUM 1680 DATFE 42 Pre-Plant Rup + DUAL 90.9 5.18 AMAGNUM 1400 DATFE 42 Pre-Plant Rup + 410P9M 89.2 5.18 A 1120 DATFE 42Pre-Plant Rup + 410P9M 88.5 5.18 A 1960 DATFE 42 Pre-Plant Rup + 410P9M87.4 5.18 A 1260 DATFE 42 Pre-Plant Rup + 410P9M 86.7 5.18 A 1680 DATFE42 Pre-Plant Rup 840 85.4 5.18 A DATFE 42 Pre-Plant Rup + DUAL 85.2 5.18A MAGNUM 1120 DATFE 42 V2 Rup + 410P9M 97.9 1.46 A 1960 DATFE 42 V2Rup + DUAL 97.2 1.46 A MAGNUM 1960 DATFE 42 V2 Rup + 410P9M 97.0 1.46 A1680 DATFE 42 V2 Rup + 410P9M 96.7 1.46 A 1260 DATFE 42 V2 Rup + 410P9M96.4 1.46 A 1120 DATFE 42 V2 Rup + DUAL 96.2 1.46 A MAGNUM 1680 DATFE 42V2 Rup + DUAL 95.7 1.46 A MAGNUM 1400 DATFE 42 V2 Rup 840 95.1 1.46 ADATFE 42 V2 Rup + DUAL 95.0 1.46 A MAGNUM 1120 TAGMI 21 At Plant Rup +DUAL 92.3 6.72 A MAGNUM 1960 TAGMI 21 At Plant Rup + DUAL 91.5 6.74 AMAGNUM 1680 TAGMI 21 At Plant Rup + DUAL 91.2 6.74 A MAGNUM 1400 TAGMI21 At Plant Rup + 410P9M 90.4 6.69 A 1960 TAGMI 21 At Plant Rup + DUAL89.9 6.67 A MAGNUM 1120 TAGMI 21 At Plant Rup + 410P9M 88.6 6.71 A 1260TAGMI 21 At Plant Rup + 410P9M 88.4 6.67 A 1120 TAGMI 21 At Plant Rup +410P9M 87.6 6.67 A 1680 TAGMI 21 At Plant Rup 840 81.2 6.78 A TAGMI 21Cracking Rup + DUAL 90.5 5.59 A MAGNUM 1960 TAGMI 21 Cracking Rup + DUAL90.0 5.57 A MAGNUM 1680 TAGMI 21 Cracking Rup + 410P9M 89.8 5.55 A 1960TAGMI 21 Cracking Rup + 410P9M 89.4 5.55 A 1680 TAGMI 21 Cracking Rup +410P9M 88.5 5.59 A 1120 TAGMI 21 Cracking Rup + DUAL 85.7 5.55 AB MAGNUM1400 TAGMI 21 Cracking Rup + DUAL 85.4 5.55 AB MAGNUM 1120 TAGMI 21Cracking Rup + 410P9M 85.1 5.65 AB 1260 TAGMI 21 Cracking Rup 840 80.25.55 B TAGMI 21 Pre-Plant Rup + 410P9M 99.6 0.91 A 1260 TAGMI 21Pre-Plant Rup + 410P9M 99.6 0.91 A 1960 TAGMI 21 Pre-Plant Rup + DUAL99.4 0.92 A MAGNUM 1120 TAGMI 21 Pre-Plant Rup + DUAL 99.3 0.91 A MAGNUM1400 TAGMI 21 Pre-Plant Rup + 410P9M 99.3 0.91 A 1680 TAGMI 21 Pre-PlantRup + DUAL 99.2 0.91 A MAGNUM 1960 TAGMI 21 Pre-Plant Rup + DUAL 99.10.91 A MAGNUM 1680 TAGMI 21 Pre-Plant Rup + 410P9M 99.0 0.91 A 1120TAGMI 21 Pre-Plant Rup 840 98.2 0.91 A TAGMI 21 V2 Rup + DUAL 98.4 2.43A MAGNUM 1960 TAGMI 21 V2 Rup + 410P9M 98.1 2.61 A 1960 TAGMI 21 V2Rup + 410P9M 98.0 2.45 A 1260 TAGMI 21 V2 Rup + 410P9M 96.5 2.40 A 1120TAGMI 21 V2 Rup + DUAL 96.1 2.42 A MAGNUM 1680 TAGMI 21 V2 Rup + 410P9M96.0 2.48 A 1680 TAGMI 21 V2 Rup + DUAL 95.1 2.40 A MAGNUM1120 TAGMI 21V2 Rup + DUAL 93.5 2.54 A MAGNUM 1400 TAGMI 21 V2 Rup 840 92.6 2.40 ATAGMI 42 At Plant Rup + DUAL 86.6 12.17 A MAGNUM 1960 TAGMI 42 At PlantRup + DUAL 81.5 12.27 A MAGNUM 1680 TAGMI 42 At Plant Rup + 410P9M 79.312.17 A 1120 TAGMI 42 At Plant Rup + DUAL 79.1 12.27 A MAGNUM 1400 TAGMI42 At Plant Rup + DUAL 77.2 12.20 A MAGNUM 1120 TAGMI 42 At Plant Rup +410P9M 77.1 12.17 A 1960 TAGMI 42 At Plant Rup + 410P9M 75.8 12.20 A1680 TAGMI 42 At Plant Rup + 410P9M 74.4 12.20 A 1260 TAGMI 42 At PlantRup 840 67.8 12.24 A TAGMI 42 Cracking Rup + DUAL 84.6 7.99 A MAGNUM1680 TAGMI 42 Cracking Rup + DUAL 83.6 8.02 A MAGNUM 1960 TAGMI 42Cracking Rup + 410P9M 81.4 7.96 A 1680 TAGMI 42 Cracking Rup + DUAL 79.98.02 A MAGNUM 1400 TAGMI 42 Cracking Rup + 410P9M 78.9 7.99 A 1120 TAGMI42 Cracking Rup + 410P9M 78.5 8.02 A 1260 TAGMI 42 Cracking Rup + 410P9M78.2 7.99 A 1960 TAGMI 42 Cracking Rup + DUAL 77.9 7.96 A MAGNUM 1120TAGMI 42 Cracking Rup 840 68.8 7.96 B TAGMI 42 Pre-Plant Rup + 410P9M84.7 8.45 A 1960 TAGMI 42 Pre-Plant Rup + DUAL 80.9 8.45 A MAGNUM 1680TAGMI 42 Pre-Plant Rup + DUAL 80.5 8.45 A MAGNUM 1960 TAGMI 42 Pre-PlantRup + 410P9M 79.8 8.45 A 1680 TAGMI 42 Pre-Plant Rup + 410P9M 77.7 8.45A 1260 TAGMI 42 Pre-Plant Rup + DUAL 76.1 8.45 A MAGNUM 1120 TAGMI 42Pre-Plant Rup + 410P9M 74.0 8.45 A 1120 TAGMI 42 Pre-Plant Rup + DUAL70.6 8.45 A MAGNUM 1400 TAGMI 42 Pre-Plant Rup 840 70.3 8.45 A TAGMI 42V2 Rup + DUAL 94.4 4.97 A MAGNUM 1960 TAGMI 42 V2 Rup + DUAL 93.9 4.92 AMAGNUM 1680 TAGMI 42 V2 Rup + DUAL 93.4 4.95 A MAGNUM 1400 TAGMI 42 V2Rup + 410P9M 92.8 4.94 A 1960 TAGMI 42 V2 Rup + 410P9M 92.0 5.03 A 1680TAGMI 42 V2 Rup + 410P9M 91.0 4.95 A 1260 TAGMI 42 V2 Rup + 410P9M 90.04.92 A 1120 TAGMI 42 V2 Rup + DUAL 86.5 4.94 A MAGNUM 1120 TAGMI 42 V2Rup 840 81.5 4.96 A

Smooth pigweed (AMACH) control was 97.2% or greater at 21 DAT for allfour application timings in these trials with field use rates of boththe encapsulated acetochlor formulation 410P9M (1260 g ai/ha) and DUALMAGNUM (1400 g ai/ha). Pre-plant, at-planting, at-cracking and earlypost applications of DUAL MAGNUM and composition 410P9M were similar at42 DAT with field use rates of each product. The early post applicationat field use rates provided 98.8% or better AMACH control at 42 DAT.

Lambsquarter (CHEAL) control was evaluated only with the at-planting andat-cracking applications. The at-planting application did not providecommercially acceptable levels of CHEAL control at 21 and 42 DAT.At-cracking applications of both DUAL MAGNUM and the encapsulatedacetochlor formulation 410P9M provided 93.6% and 95.5% efficacy,respectively, at 21 DAT. At the later sampling date, 42 DAT, theat-cracking application provided 85.4-85.9% for CHEAL.

Datura (DATFE) efficacy was similar for the encapsulated acetochlorformulation 410P9M and DUAL MAGNUM at field application rates for allfour application timings at 21 DAT. DATFE efficacy was 90.2% or greaterwith these application rates. At 42 DAT, DATFE efficacy was similar forboth composition 410P9M and DUAL MAGNUM at field use rates with all fourapplication timings and efficacy was 87.4% or greater.

Wild marigold (TAGMI) efficacy was similar for both DUAL MAGNUM andcomposition 410P9M at the early pre-plant application with 99.3-99.6%control at 21 DAT using field use rates of each product. At-plantingapplications of DUAL MAGNUM provided 91.2% control, which was similar tothe control achieved with composition 410P9M with 88.6% TAGMI efficacy.Early post application of composition 410P9M at 1260 g ai/ha provided98.0% efficacy, which was similar to the 93.5% control provided by DUALMAGNUM at 1400 g ai/ha. The pre-planting, at-planting, and at-crackingapplication of composition 410P9M and DUAL MAGNUM provided less than80.0% TAGMI efficacy at 42 DAT. The early post applications provided91.0% efficacy for 410P9M and 93.4% for DUAL MAGNUM at 42 DAT.

Example 10. Preparation of Aqueous Dispersions of MicroencapsulatedAcetochlor

Various aqueous dispersions of microencapsulated acetochlor wereprepared. The formulations were prepared using an amine component (TETAor a combination of TETA and XDA) and an isocyanate component (DES N3200or MISTAFLEX, which is a blend of polyisocyanates comprising DES N3200and DES W). Typically, the formulations contain an internal phasesolvents such as NORPAR 15, ISOPAR V, ISOPAR L, EXXSOL D-130, or EXXSOLD-110, with the exception of formulations 2805A, 2805B, and 2805C. Theformulations were prepared using an excess of amine equivalents. Toprepare these formulations, batches of each of the internal phase, theexternal phase, the amine solution, and the stabilizer solution wereprepared containing the components and amounts shown in the table below.

The aqueous dispersions of microcapsules were prepared substantially asdescribed above in Example 1. The amine solutions were used to initiatepolymerization. During emulsification, the mixer speed was varied bycontrolling the blender to achieve mean particle sizes as shown in theparticle size table below. The particle size parameters were measuredusing a Beckman Coulter LS Particle Size Analyzer.

The acetochlor loading was varied among the formulations. For example,in formulations 609A, 609B, 609C, 660A, 660B, 660C, 664A, 664B, 664C,668A, 668B, 668C, 672A, 672B, 672C, 680A, 680B, 680C, 684A, 684B, 684C,and 684D, the acetochlor loading was approximately 33% by weight, whichis relatively lower than the acetochlor loading in DEGREE. Informulations 993A, 993B, and 993C, the acetochlor loading wasapproximately 38% by weight, which is relatively lower than theacetochlor loading in DEGREE. In formulations 997A, 997B, and 997C, theacetochlor loading was approximately 40% by weight, which is relativelylower than the acetochlor loading in DEGREE. In formulations 601A, 601B,and 601C, the acetochlor loading was approximately equal to DEGREE.

The proportion of shell wall components was varied among theformulations. For example, formulations 613A, 613B, and 613C wereprepared using a higher proportion of shell wall components compared tocommercially available DEGREE. The formulation for DEGREE employs about8% by weight shell wall components compared to the acetochlor loading.By comparison, formulations 613A, 613B, and 613C were prepared with 16%by weight shell wall components compared to the acetochlor loading.Formulations 617A, 617B, and 617C were prepared using a similar relativeproportion of shell wall components compared to DEGREE. Formulations621A, 621B, 621C, and 621D were prepared using a higher proportion ofshell wall components compared to DEGREE, but a lower proportioncompared to formulations 613A, 613B, and 613C. Formulations 621A, 621B,621C, and 621D were prepared with 12% by weight shell wall componentscompared to the acetochlor loading.

The weight ratio of acetochlor and internal phase solvent was alsovaried among the formulations. For example, the weight ratio ofacetochlor to NORPAR 15 diluent was approximately 16:1 in formulations684A, 684B, 684C, and 684D compared to about 19:1 in the formulations680A, 680B, and 680C.

TABLE Formulation Components Internal Phase Molar Iso- External PhaseRatio Solvent cyanate Sokalan Ammonium Amine:Iso- Acetochlor mass massGlycerin CP9 Caseinate Acid Water Form. cyanate (g) Solvent (g)Isocyanate (g) (g) (g) (g) (g) (g) 3993 1.29:1 175.0 NORPAR 9.3 DESN3200 13.01 32.5 9.45 0.19 0.72 115.0 15 3995 1.26:1 175.0 NORPAR 9.3DES N3200 12.87 32.0 9.48 0.19 0.75 115.0 15 3997 1.25:1 175.0 NORPAR9.11 DES N3200 12.79 32.0 9.41 0.19 0.72 115.0 15 2805A 1.03:1-1.04  530.0 — — DES N3200, 31.99, 5.65  104.0 30.6 0.60 2.22 373.0 DES W 2805B1.03:1-1.04   530.0 — — DES N3200, 31.99, 5.65  104.0 30.6 0.60 2.22373.0 DES W 2805C 1.03:1-1.04   530.0 — — DES N3200, 31.99, 5.65  104.030.6 0.60 2.22 373.0 DES W 831A 1.04:1-1.05:1 504.01 NORPAR 26.27MISTAFLEX 36.60 103.05 30.38 0.61 2.35 372.01 15 H9915 831B1.04:1-1.05:1 504.01 NORPAR 26.27 MISTAFLEX 36.60 103.05 30.38 0.61 2.35372.01 15 H9915 831D 1.04:1-1.05:1 504.01 NORPAR 26.27 MISTAFLEX 36.60103.05 30.38 0.61 2.35 372.01 15 H9915 838A 1.04:1-1.05:1 669.0 NORPAR34.92 MISTAFLEX 49.10 137.0 40.45 0.81 3.10 494.00 15 H9915 838B1.04:1-1.05:1 669.0 NORPAR 34.92 MISTAFLEX 49.10 137.0 40.45 0.81 3.10494.00 15 H9915 838C 1.04:1-1.05:1 669.0 NORPAR 34.92 MISTAFLEX 49.10137.0 40.45 0.81 3.10 494.00 15 H9915 838D 1.04:1-1.05:1 669.0 NORPAR34.92 MISTAFLEX 49.10 137.0 40.45 0.81 3.10 494.00 15 H9915 843A1.04:1-1.05:1 669.0 NORPAR 35.0 MISTAFLEX 49.58 137.10 40.4 0.81 3.0494.02 15 H9915 843B 1.04:1-1.05:1 669.0 NORPAR 35.0 MISTAFLEX 49.58137.10 40.40 0.81 3.0 494.02 15 H9915 843C 1.04:1-1.05:1 669.0 NORPAR35.0 MISTAFLEX 49.58 137.10 40.40 0.81 3.0 494.02 15 H9915 843D1.04:1-1.05:1 669.0 NORPAR 35.0 MISTAFLEX 49.58 137.10 40.40 0.81 3.0494.02 15 H9915 874A  1.2:1 352.70 NORPAR 18.43 MISTAFLEX 25.73 64.6019.06 0.38 1.39 232.80 15 H9916 874B  1.2:1 352.70 NORPAR 18.43MISTAFLEX 25.73 64.60 19.06 0.38 1.39 232.80 15 H9917 877A  1.1:1 353.0NORPAR 18.43 MISTAFLEX 26.30 64.69 19.1 0.38 1.40 233.08 15 H9915 877B 1.1:1 353.0 NORPAR 18.43 MISTAFLEX 26.30 64.69 19.1 0.38 1.40 233.08 15H9915 880A  1.3:1 353.0 NORPAR 18.42 MISTAFLEX 25.33 64.50 19.05 0.371.40 232.5 15 H9915 880B  1.3:1 353.0 NORPAR 18.42 MISTAFLEX 25.33 64.5019.05 0.37 1.40 232.5 15 H9915 883A 1.15:1 352.75 NORPAR 18.44 MISTAFLEX25.97 64.65 19.07 0.38 1.37 232.92 15 H9915 885A 1.25:1 174.18 NORPAR9.10 MISTAFLEX 12.65 32.0 9.4 0.19 0.70 115.0 15 H9915 911A  1.2:1 352.7NORPAR 18.41 DES N3200, 12.59, 12.59 64.50 19.0 0.4 1.39 232.3 15 DES W911B  1.2:1 352.7 NORPAR 18.41 DES N3200, 12.59, 12.59 64.50 19.0 0.41.39 232.3 15 DES W 914A  1.2:1 352.70 NORPAR 18.40 DES N3200, 21.99,4.0  64.60 19.1 0.4 1.38 232.77 15 DES W 914C  1.2:1 352.70 NORPAR 18.40DES N3200, 21.99, 4.0  64.60 19.1 0.4 1.38 232.77 15 DES W 917A  1.2:1352.65 NORPAR 18.40 DES N3200, 17.85, 7.66  64.57 19.01 0.38 1.41 232.6015 DES W 917B  1.2:1 352.65 NORPAR 18.40 DES N3200, 17.85, 7.66  64.5719.01 0.38 1.41 232.60 15 DES W 934 1.05:1 175.50 ISOPAR L 9.10MISTAFLEX 13.06 32.0 9.57 0.20 0.75 116.0 H9915 939 1.05:1 174.20 ISOPARL 18.20 MISTAFLEX 13.70 30.00 8.90 0.18 0.75 108.0 H9915 936A 1.05:1352.70 ISOPAR L 18.40 MISTAFLEX 26.40 64.70 19.10 0.38 1.42 233.3 H9915936B 1.05:1 352.70 ISOPAR L 18.40 MISTAFLEX 26.40 64.70 19.10 0.38 1.42233.3 H9915 941A 1.05:1 529.0 ISOPAR V 55.30 MISTAFLEX 41.60 90.90 26.800.54 2.09 327.60 H9915 941B 1.05:1 529.0 ISOPAR V 55.30 MISTAFLEX 41.6090.90 26.80 0.54 2.09 327.60 H9915 941C 1.05:1 529.0 ISOPAR V 55.30MISTAFLEX 41.60 90.90 26.80 0.54 2.09 327.60 H9915 945A 1.05:1 529.0ISOPAR V 27.65 MISTAFLEX 39.60 97.1 28.70 0.57 2.25 350.0 H9915 945B1.05:1 529.0 ISOPAR V 27.65 MISTAFLEX 39.60 97.1 28.70 0.57 2.25 350.0H9915 945C 1.05:1 529.0 ISOPAR V 27.65 MISTAFLEX 39.60 97.1 28.70 0.572.25 350.0 H9915 949 1.05:1 174.25 Exxsol 9.1 MISTAFLEX 13.1 32.0 9.50.2 0.75 115.3 D-130 H9915 951A 1.05:1 352.70 ISOPAR V 18.42 MISTAFLEX26.40 64.70 19.10 0.39 1.45 233.3 H9915 951B 1.05:1 352.70 ISOPAR V18.42 MISTAFLEX 26.40 64.70 19.10 0.39 1.45 233.3 H9915 954A 1.05:1352.7 Exxsol 36.85 MISTAFLEX 27.71 60.80 17.9 0.37 1.28 218.39 D-130954B 1.05:1 352.7 Exxsol 36.85 MISTAFLEX 27.71 60.80 17.9 0.37 1.28218.39 D-130 957A 1.05:1 353.0 ISOPAR L 36.90 MISTAFLEX 27.7 60.6 17.90.37 1.35 218.40 H9915 957B 1.05:1 353.0 ISOPAR L 36.90 MISTAFLEX 27.760.6 17.9 0.37 1.35 218.40 H9915 960A 1.05:1 352.70 Exxsol 36.83MISTAFLEX 27.70 60.6 17.9 0.37 1.35 218.40 D-130 H9915 960B 1.05:1352.70 Exxsol 36.83 MISTAFLEX 27.70 60.6 17.9 0.37 1.35 218.40 D-130H9915 993A  1.2:1 483.0 NORPAR 25.0 MISTAFLEX 35.20 108.0 31.82 0.642.40 389.0 15 H9915 993B  1.2:1 483.0 NORPAR 25.0 MISTAFLEX 35.20 108.031.82 0.64 2.40 389.0 15 H9915 993C  1.2:1 483.0 NORPAR 25.0 MISTAFLEX35.20 108.0 31.82 0.64 2.40 389.0 15 H9915 997A  1.2:1 508.40 NORPAR26.30 MISTAFLEX 37.10 101.90 30.05 0.61 2.25 367.0 15 H9915 997B  1.2:1508.40 NORPAR 26.30 MISTAFLEX 37.10 101.90 30.05 0.61 2.25 367.0 15H9915 997C  1.2:1 508.40 NORPAR 26.30 MISTAFLEX 37.10 101.90 30.05 0.612.25 367.0 15 H9915 601A  1.2:1 534.60 NORPAR 27.65 MISTAFLEX 39.0 95.6628.22 0.58 2.25 345.0 15 H9915 601B  1.2:1 534.60 NORPAR 27.65 MISTAFLEX39.0 95.66 28.22 0.58 2.25 345.0 15 H9915 601C  1.2:1 534.60 NORPAR27.65 MISTAFLEX 39.0 95.66 28.22 0.58 2.25 345.0 15 H9915 609A  1.2:1418.10 NORPAR 21.70 MISTAFLEX 30.56 123.10 36.32 0.74 2.84 443.6 15H9915 609B  1.2:1 418.10 NORPAR 21.70 MISTAFLEX 30.56 123.10 36.32 0.742.84 443.6 15 H9915 609C  1.2:1 418.10 NORPAR 21.70 MISTAFLEX 30.56123.10 36.32 0.74 2.84 443.6 15 H9915 613A  1.2:1 507.0 NORPAR 26.30MISTAFLEX 81.01 88.81 26.2 0.52 1.96 320.0 15 H9915 613B  1.2:1 507.0NORPAR 26.30 MISTAFLEX 81.01 88.81 26.2 0.52 1.96 320.0 15 H9915 613C 1.2:1 507.0 NORPAR 26.30 MISTAFLEX 81.01 88.81 26.2 0.52 1.96 320.0 15H9915 617A 1.25:1 506.78 NORPAR 26.33 MISTAFLEX 35.48 102.2 31.1 0.622.85 368.3 15 H9915 617B 1.25:1 506.78 NORPAR 26.33 MISTAFLEX 35.48102.2 31.1 0.62 2.85 368.3 15 H9915 617C 1.25:1 506.78 NORPAR 26.33MISTAFLEX 35.48 102.2 31.1 0.62 2.85 368.3 15 H9915 621A  1.2:1 675.72NORPAR 35.10 MISTAFLEX 77.3 127.6 37.90 0.25 3.0 461.0 15 H9915 621B 1.2:1 675.72 NORPAR 35.10 MISTAFLEX 77.3 127.6 37.90 0.25 3.0 461.0 15H9915 621C  1.2:1 675.72 NORPAR 35.10 MISTAFLEX 77.3 127.6 37.90 0.253.0 461.0 15 H9915 621D  1.2:1 675.72 NORPAR 35.10 MISTAFLEX 77.3 127.637.90 0.25 3.0 461.0 15 H9915 660A  1.2:1 524.1 NORPAR 27.0 MISTAFLEX38.32 146.40 43.22 0.88 3.15 527.40 15 H9915 660B  1.2:1 524.1 NORPAR27.0 MISTAFLEX 38.32 146.40 43.22 0.88 3.15 527.40 15 H9915 660C  1.2:1524.1 NORPAR 27.0 MISTAFLEX 38.32 146.40 43.22 0.88 3.15 527.40 15 H9915664A  1.2:1 524.10 ISOPAR L 54.10 MISTAFLEX 40.15 140.40 41.40 — 3.10506.0 H9915 664B  1.2:1 524.10 ISOPAR L 54.10 MISTAFLEX 40.15 140.4041.40 — 3.10 506.0 H9915 664C  1.2:1 524.10 ISOPAR L 54.10 MISTAFLEX40.15 140.40 41.40 — 3.10 506.0 H9915 668A  1.2:1 524.10 Exxsol 54.10MISTAFLEX 40.15 140.30 41.40 0.85 3.05 506.0 D-110 H9915 668B  1.2:1524.10 Exxsol 54.10 MISTAFLEX 40.15 140.30 41.40 0.85 3.05 506.0 D-110H9915 668C  1.2:1 524.10 Exxsol 54.10 MISTAFLEX 40.15 140.30 41.40 0.853.05 506.0 D-110 H9915 672A  1.2:1 524.1 ISOPAR V 27.1 MISTAFLEX 38.3146.4 43.2 0.88 3.25 521.4 H9915 672B  1.2:1 524.1 ISOPAR V 27.1MISTAFLEX 38.3 146.4 43.2 0.88 3.25 521.4 H9915 672C  1.2:1 524.1 ISOPARV 27.1 MISTAFLEX 38.3 146.4 43.2 0.88 3.25 521.4 H9915 680A  1.2:1524.10 NORPAR 27.10 MISTAFLEX 38.3 146.4 43.20 0.88 3.50 527.40 15 H9915680B  1.2:1 524.10 NORPAR 27.10 MISTAFLEX 38.3 146.4 43.20 0.88 3.50527.40 15 H9915 680C  1.2:1 524.10 NORPAR 27.10 MISTAFLEX 38.3 146.443.20 0.88 3.50 527.40 15 H9915 684A  1.2:1 524.10 NORPAR 32.50MISTAFLEX 38.60 145.2 42.90 0.88 3.30 523.0 15 H9915 684B  1.2:1 524.10NORPAR 32.50 MISTAFLEX 38.60 145.2 42.90 0.88 3.30 523.0 15 H9915 684C 1.2:1 524.10 NORPAR 32.50 MISTAFLEX 38.60 145.2 42.90 0.88 3.30 523.015 H9915 External Phase TETA, Xylylene- Stabilizer 50% diamine, KelzanAnti- Proxel sol. 50% sol. Invalon CC foam Glycerin GXL Caustic BufferForm. (g) (g) (g) (g) (g) (g) (g) (g) (g) 3993 6.71 — 23.65 0.21 0.015.85 0.21 0.07 0.47 3995 6.5 — 23.65 0.21 0.0 15.85 0.21 0.07 0.47 39976.4 — 23.65 0.21 0.0 15.85 0.21 0.07 0.47 2805A 5.48 — 71.83 0.64 0.0148.15 0.64 0.22 1.43 2805B 5.50 — 71.83 0.64 0.01 48.15 0.64 0.22 1.432805C 5.39 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 831A 4.35 1.90 71.830.01 0.22 0.64 48.15 0.64 1.43 831B 4.38 1.91 71.83 0.01 0.22 0.64 48.150.64 1.43 831D 4.37 1.87 71.83 0.01 0.22 0.64 48.15 0.64 1.43 838A 4.801.2 95.48 0.02 0.29 0.86 64.0 0.86 1.91 838B 4.79 1.21 95.48 0.02 0.290.86 64.0 0.86 1.91 838C 4.78 1.22 95.48 0.02 0.29 0.86 64.0 0.86 1.91838D 4.80 1.21 95.48 0.02 0.29 0.86 64.0 0.86 1.91 843A 5.17 0.59 95.480.02 0.29 0.86 64.0 0.86 1.91 843B 5.18 0.6 95.48 0.02 0.29 0.86 64.00.86 1.91 843C 5.16 0.58 95.48 0.02 0.29 0.86 64.0 0.86 1.91 843D 5.170.59 95.48 0.02 0.29 0.86 64.0 0.86 1.91 874A 6.46 — 47.89 0.01 0.150.43 32.10 0.43 0.96 874B 6.45 — 47.89 0.01 0.15 0.43 32.10 0.43 0.96877A 6.02 — 47.89 0.01 0.15 0.43 32.10 0.43 0.96 877B 6.02 — 47.89 0.010.15 0.43 32.10 0.43 0.96 880A 6.88 — 47.89 0.01 0.15 0.43 32.10 0.430.96 880B 6.87 — 47.89 0.01 0.15 0.43 32.10 0.43 0.96 883A 12.63 — 47.890.43 0.01 32.10 0.43 0.15 0.96 885A 6.67 — 23.65 0.21 0.0 15.85 0.210.07 0.47 911A 7.1 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 911B 7.1 —47.89 0.43 0.01 32.10 0.43 0.15 0.96 914A 6.46 — 47.89 0.43 0.01 32.100.43 0.15 0.96 914C 6.46 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 917A6.74 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 917B 6.74 — 47.89 0.43 0.0132.10 0.43 0.15 0.96 934 5.79 — 23.65 0.21 0.0 15.85 0.21 0.07 0.47 9396.08 — 23.65 0.21 0.0 15.85 0.21 0.07 0.47 936A 5.79 — 47.89 0.43 0.0132.10 0.43 0.15 0.96 936B 5.79 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96941A 6.09 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 941B 6.10 — 71.83 0.640.01 48.15 0.64 0.22 1.43 941C 6.10 — 71.83 0.64 0.01 48.15 0.64 0.221.43 945A 17.6 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 945B 17.6 — 71.830.64 0.01 48.15 0.64 0.22 1.43 945C 17.6 — 71.83 0.64 0.01 48.15 0.640.22 1.43 949 5.8 — 23.65 0.21 0.0 15.85 0.21 0.07 0.47 951A 11.73 —47.89 0.43 0.01 32.10 0.43 0.15 0.96 951B 11.73 — 47.89 0.43 0.01 32.100.43 0.15 0.96 954A 12.31 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 954B12.31 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 957A 12.31 — 47.89 0.430.01 32.10 0.43 0.15 0.96 957B 12.31 — 47.89 0.43 0.01 32.10 0.43 0.150.96 960A 6.10 — 47.89 0.43 0.01 32.10 0.43 0.15 0.96 960B 6.09 — 47.890.43 0.01 32.10 0.43 0.15 0.96 993A 5.90 — 71.83 0.64 0.01 48.15 0.640.22 1.43 993B 5.87 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 993C 5.86 —71.83 0.64 0.01 48.15 0.64 0.22 1.43 997A 6.21 — 71.83 0.64 0.01 48.150.64 0.22 1.43 997B 6.23 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 997C6.22 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 601A 6.54 — 71.83 0.64 0.0148.15 0.64 0.22 1.43 601B 6.53 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43601C 6.54 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 609A 5.12 — 71.83 0.640.01 48.15 0.64 0.22 1.43 609B 5.11 — 71.83 0.64 0.01 48.15 0.64 0.221.43 609C 5.13 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 613A 13.56 — 71.830.64 0.01 48.15 0.64 0.22 1.43 613B 13.56 — 71.83 0.64 0.01 48.15 0.640.22 1.43 613C 13.57 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 617A 6.20 —71.83 0.64 0.01 48.15 0.64 0.22 1.43 617B 6.20 — 71.83 0.64 0.01 48.150.64 0.22 1.43 617C 6.21 — 71.83 0.64 0.01 48.15 0.64 0.22 1.43 621A9.72 — 95.77 0.86 0.02 64.20 0.86 0.29 1.91 621B 9.72 — 95.77 0.86 0.0264.20 0.86 0.29 1.91 621C 9.72 — 95.77 0.86 0.02 64.20 0.86 0.29 1.91621D 9.73 — 95.77 0.86 0.02 64.20 0.86 0.29 1.91 660A 6.43 — 108.38 0.970.02 72.65 0.97 0.33 2.16 660B 6.42 — 108.38 0.97 0.02 72.65 0.97 0.332.16 660C 6.45 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 664A 6.75 —108.38 0.97 0.02 72.65 0.97 0.33 2.16 664B 6.75 — 108.38 0.97 0.02 72.650.97 0.33 2.16 664C 6.74 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 668A20.36 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 668B 20.36 — 108.38 0.970.02 72.65 0.97 0.33 2.16 668C 20.36 — 108.38 0.97 0.02 72.65 0.97 0.332.16 672A 6.40 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 672B 6.42 —108.38 0.97 0.02 72.65 0.97 0.33 2.16 672C 6.43 — 108.38 0.97 0.02 72.650.97 0.33 2.16 680A 6.42 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 680B6.43 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 680C 6.42 — 108.38 0.970.02 72.65 0.97 0.33 2.16 684A 6.49 — 108.38 0.97 0.02 72.65 0.97 0.332.16 684B 6.48 — 108.38 0.97 0.02 72.65 0.97 0.33 2.16 684C 6.49 —108.38 0.97 0.02 72.65 0.97 0.33 2.16

TABLE Particle Size Parameters Mean Particle Standard size DeviationFormulation (μm) (μm) 3993   2.01 1.14 3995   9.49 6.31 3997   10.8 7.92805A  2.26 1.27 2805B  9.73 6.33 2805C  15.89 12.51 831A 2.11 1.22 831B8.48 5.82 831D 11.7 — 838A 2.06 1.12 838B 6.74 4.44 838C 12.84 8.16 838D8.35 5.49 843A 2.18 1.16 843B 7.62 5.05 843C 11.68 7.92 843D 5.58 3.74874A 2.02 1.06 874B 7.33 7.93 877A 2.08 1.13 877B 7.68 5.14 880A 2.171.15 880B 8.21 5.20 883A 2.27 2.28 885A 1.94 1.06 911A 7.73 5.64 911B2.62 2.94 914A 2.21 1.25 914C 7.43 5.05 917A 1.99 1.1 917B 7.55 5.01934  10.69 8.33 939  9.75 5.96 936A 10.16 6.34 936B 8.36 5.46 941A 8.905.56 941B 11.67 6.76 941C 10.98 6.52 945A 9.72 6.02 945B 13.22 8.23 945C12.48 7.84 949  10.59 6.45 951A 11.28 7.53 951B 8.30 5.48 954A 9.83 6.04954B 7.7 — 957A 10.46 6.38 957B 8.01 5.13 960A 10.60 6.51 960B 6.65 4.55993A 7.86 5.36 993B 10.95 6.64 993C 13.9 10.4 997A 7.73 5.17 997B 10.566.66 997C 13.38 9.21 601A 8.13 5.23 601B 11.08 7.44 601C 14.64 10.46609A 3.28 2.63 609B 11.61 7.22 609C 12.65 7.66 613A 3.24 3.37 613B 7.735.18 613C 10.90 7.88 617A 7.10 4.67 617B 8.93 5.75 617C 11.23 6.86 621A6.70 4.42 621B 8.88 5.89 621C 2.48 2.43 621D 11.53 7.02 660A 12.50 8.59660B 10.13 7.69 660C 6.83 4.77 664A 6.84 5.24 664B 8.27 5.47 664C 9.355.95 668A 6.75 4.55 668B 7.02 4.75 668C 9.75 6.16 672A 8.13 5.35 672B8.82 5.71 672C 10.82 7.59 680A 9.29 6.08 680B 7.60 5.04 680C 6.70 4.51684A 8.36 5.59 684B 7.04 4.78 684C 6.33 4.35 684D 10.3 —

Example 11. Release Rates of Microencapsulated Acetochlor Formulations

The release rates for some of the formulations prepared above in Example10 were measured according to the above described protocol wherein adispersion of 1% by weight of the encapsulated acetochlor in deionizedwater was agitated at 150 RPM and 25° C. in a SOTAX AT-7 agitateddissolution test apparatus and sampled at 6 hours and 24 hours. Therelease rates of the tested formulations are reported in the followingtable. For comparison, the release rates from DEGREE formulations werealso measured and reported.

TABLE Release Rates Release at 6 Release at 24 Formulation hours (ppm)hours (ppm) 3993   211 280 3995   80 104 3997   96 128 2805A  179 3122805B  91 152 2805C  88 140 DEGREE 129 200 DEGREE 123 200 831A 245 305831B 168 191 831D 156 182 838A 186 275 838D 170 214 838C 73 90 843A 188286 843B 94 123 843C 96 134 DEGREE 131 202 DEGREE 136 200 911A 137 146911B 307 320 914A 221 321 914C 96 136 917A 278 329 917B 93 125 DEGREE130 202 934  58 73 936B 70 90 941C 52 63 951B 78 95 954B 54 63 DEGREE129 179 960A 52 64 DEGREE 129 179 941A 56 64 954A 53 64 957B 68 87 960B70 86 DEGREE 129 179 936B 70 90 951B 78 95 960A 52 64 960B 70 86 DEGREE129 179 957B 68 87 960B 70 86 951B 78 95 936B 70 90 DEGREE 129 179 993A81 108 993B 64 86 993C 50 69 997A 79 106 997C 53 73 601C 74 94 DEGREE134 217 613B 52 65 613C 45 55 617A 77 97 617B 79 95 621A 100 123 621B 6582 DEGREE 127 182 DEGREE 118 174 664A 98 118 664B 75 89 664C 68 83 668B81 94 668C 59 69 660C 118 144 680A 67 79 680B 82 106 680C 78 103 684A 6992 684C 62 78 684D 80 104

When introducing elements of the present invention or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

In view of the above, it will be seen that the several objects of theinvention are achieved and other advantageous results attained.

As various changes could be made in the above compositions and methodswithout departing from the scope of the invention, it is intended thatall matter contained in the above description shall be interpreted asillustrative and not in a limiting sense.

What is claimed is:
 1. A method for preparing an acetamide herbicidecomposition, the method comprising: preparing a first population of aparticulate microencapsulated acetamide herbicide comprising awater-immiscible core material comprising the acetamide herbicide and amicrocapsule containing the core material and having a shell wallcomprising a polyurea, wherein the first population of the particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 3 μm to about 11 μm; preparing a second population of theparticulate microencapsulated acetamide herbicide comprising awater-immiscible core material comprising the acetamide herbicide and amicrocapsule containing the core material and having a shell wallcomprising a polyurea, wherein the second population of the particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 12 μm to about 20 μm; and combining the first population of theparticulate microencapsulated acetamide herbicide and the secondpopulation of the particulate microencapsulated acetamide herbicide toform the acetamide herbicide composition; wherein the acetamideherbicide comprises acetochlor.
 2. The method of claim 1 wherein theweight ratio of the first population of the particulatemicroencapsulated acetamide herbicide to the second population of theparticulate microencapsulated acetamide herbicide is from about 10:1 toabout 1:10.
 3. The method of claim 1 wherein the weight ratio of thefirst population of the particulate microencapsulated acetamideherbicide to the second population of the particulate microencapsulatedacetamide herbicide is from about 5:1 to about 1:5.
 4. The method ofclaim 1 wherein the acetamide herbicide composition exhibits amulti-modal acetamide herbicide release profile.
 5. A method forpreparing an acetamide herbicide composition, the method comprising:preparing a first population of a particulate microencapsulatedacetamide herbicide comprising a water-immiscible core materialcomprising the acetamide herbicide and a microcapsule containing thecore material and having a shell wall comprising a polyurea, wherein thefirst population of the particulate microencapsulated acetamideherbicide has a mean particle size of from about 3 μm to about 11 μm;preparing a second population of the particulate microencapsulatedacetamide herbicide comprising a water-immiscible core materialcomprising the acetamide herbicide and a microcapsule containing thecore material and having a shell wall comprising a polyurea, wherein thesecond population of the particulate microencapsulated acetamideherbicide has a mean particle size of from about 12 μm to about 20 μm;and combining the first population of the particulate microencapsulatedacetamide herbicide and the second population of the particulatemicroencapsulated acetamide herbicide to form the acetamide herbicidecomposition; wherein the shell wall of the particulate microencapsulatedacetamide herbicide is formed in a polymerization medium by apolymerization reaction between a polyisocyanate component comprising apolyisocyanate or mixture of polyisocyanates and a polyamine componentcomprising a polyamine or mixture of polyamines to form the polyurea andwherein the ratio of amine molar equivalents contained in the polyaminecomponent to isocyanate molar equivalents contained in thepolyisocyanate component in the polymerization medium used to form theshell wall in at least one of the first and second populations of theparticulate microencapsulated acetamide herbicide is from about 1.1:1 toabout 1.7:1; and wherein the acetamide herbicide comprises acetochlor.6. A method for preparing an acetamide herbicide composition, the methodcomprising: preparing a first population of a particulatemicroencapsulated acetamide herbicide comprising a water-immiscible corematerial comprising the acetamide herbicide and a microcapsulecontaining the core material and having a shell wall comprising apolyurea, wherein the first population of the particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 3 μm to about 11 μm; preparing a second population of theparticulate microencapsulated acetamide herbicide comprising awater-immiscible core material comprising the acetamide herbicide and amicrocapsule containing the core material and having a shell wallcomprising a polyurea, wherein the second population of the particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 12 μm to about 20 μm; and combining the first population of theparticulate microencapsulated acetamide herbicide and the secondpopulation of the particulate microencapsulated acetamide herbicide toform the acetamide herbicide composition; wherein the shell wall of theparticulate microencapsulated acetamide herbicide is formed in apolymerization medium by a polymerization reaction between apolyisocyanate component comprising a polyisocyanate or mixture ofpolyisocyanates and a polyamine component comprising a polyamine ormixture of polyamines to form the polyurea and wherein the ratio ofamine molar equivalents contained in the polyamine component toisocyanate molar equivalents contained in the polyisocyanate componentin the polymerization medium used to form the shell wall in at least oneof the first and second populations of the particulate microencapsulatedacetamide herbicide is from about 1.5:1 to about 1.7:1; and wherein theacetamide herbicide comprises acetochlor.
 7. The method of claim 1wherein the first population of the particulate microencapsulatedacetamide herbicide has a mean particle size of from about 4 μm to about11 μm and the second population of the particulate microencapsulatedacetamide herbicide has a mean particle size of from about 12 μm toabout 18 μm.
 8. The method of claim 1 wherein the acetamide herbicidefurther comprises an additional acetamide herbicide selected from thegroup consisting of alachlor, butachlor, butenachlor, delachlor,diethatyl, dimethachlor, dimethenamid, dimethenamid-P, mefenacet,metazochlor, metolachlor, S-metolachlor, napropamide, pretilachlor,pronamide, propachlor, propisochlor, prynachlor, terbuchlor, thenylchlorand xylachlor, salts and esters thereof, and mixtures thereof.
 9. Themethod of claim 1 wherein the acetamide herbicide is acetochlor.
 10. Themethod of claim 1 wherein the acetamide herbicide composition comprisesless than about 62.5 wt % microcapsules of the particulatemicroencapsulated acetamide herbicide.
 11. The method of claim 1 whereinthe acetamide herbicide composition comprises less than about 55 wt %microcapsules of the particulate microencapsulated acetamide herbicide.12. The method of claim 1 wherein the acetamide herbicide compositioncomprises at least 30 wt % microcapsules of the particulatemicroencapsulated acetamide herbicide.
 13. The method of claim 1 whereinthe acetamide herbicide loading of the composition is from about 5 wt %to about 50 wt % on an active ingredient basis.
 14. The method of claim1 wherein the acetamide herbicide composition further comprises one ormore co-herbicides.
 15. The method of claim 14 wherein the co-herbicideis selected from acetyl CoA carboxylase inhibitors, enolpyruvylshikimate-3-phosphate synthase inhibitors, glutamine synthetaseinhibitors, synthetic auxins, photosystem II inhibitors, acetolactatesynthase or acetohydroxy acid synthase inhibitors, photosystem Iinhibitors, mitosis inhibitors, protoporphyrinogen oxidase inhibitors,cellulose inhibitors, oxidative phosphorylation uncouplers,dihydropteroate synthase inhibitors, fatty acid and lipid biosynthesisinhibitors, auxin transport inhibitors and carotenoid biosynthesisinhibitors, salts and esters thereof, racemic mixtures and resolvedisomers thereof, and mixtures thereof.
 16. The method of claim 14wherein the co-herbicide is not encapsulated.
 17. The method of claim 1wherein the acetamide herbicide composition is diluted to form anapplication mixture.
 18. The method of claim 14 wherein the co-herbicideis selected from the group consisting of glyphosate, glufosinate,flumioxazin, fomesafen, lactofen, sulfentrazone, oxyfluorfen,saflufenacil, metribuzin and fluometuron, salts and esters thereof,racemic mixtures and resolved isomers thereof, and mixtures thereof. 19.The method of claim 15 wherein the co-herbicide is a synthetic auxinherbicide selected from the group consisting of 2,4-D, 2,4-DB,dichloroprop, MCPA, MCPB, aminopyralid, clopyralid, fluroxypyr,triclopyr, diclopyr, mecoprop, dicamba, picloram and quinclorac, saltsand esters thereof, and combinations thereof.
 20. The method of claim 15wherein the co-herbicide is a photosystem II inhibitor selected from thegroup consisting of ametryn, amicarbazone, atrazine, bentazon, bromacil,bromoxynil, chlorotoluron, cyanazine, desmedipham, desmetryn, dimefuron,diuron, fluometuron, hexazinone, ioxynil, isoproturon, linuron,metamitron, methibenzuron, metoxuron, metribuzin, monolinuron,phenmedipham, prometon, prometryn, propanil, pyrazon, pyridate, siduron,simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazineand trietazine, salts and esters thereof, and mixtures thereof.
 21. Themethod of claim 15 wherein the co-herbicide is a protoporphyrinogenoxidase inhibitor selected from the group consisting of acifluorfen,azafenidin, bifenox, butafenacil, carfentrazone-ethyl, flufenpyr-ethyl,flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen,fluthiacet-methyl, fomesafen, lactofen, oxadiargyl, oxadiazon,oxyfluorfen, pyraflufen-ethyl, saflufenacil and sulfentrazone, salts andesters thereof, and mixtures thereof.
 22. The method of claim 15 whereinthe co-herbicide is a carotenoid biosynthesis inhibitor selected fromthe group consisting of aclonifen, amitrole, beflubutamid, benzofenap,clomazone, diflufenican, fluridone, flurochloridone, flurtamone,isoxaflutole, mesotrione, norflurazon, picolinafen, pyrazolynate,pyrazoxyfen, sulcotrione, tembotrione and topramezone, salts and estersthereof, and combinations thereof.
 23. The method of claim 1 wherein thefirst population of particulate microencapsulated acetamide herbicidehas a mean particle size of from about 8 μm to about 11 μm and thesecond population of particulate microencapsulated acetamide herbicidehas a mean particle size of from about 11.5 μm to about 14 μm.
 24. Themethod of claim 5 wherein the first population of particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 8 μm to about 11 μm and the second population of particulatemicroencapsulated acetamide herbicide has a mean particle size of fromabout 11.5 μm to about 14 μm.
 25. The method of claim 6 wherein thefirst population of particulate microencapsulated acetamide herbicidehas a mean particle size of from about 8 μm to about 11 μm and thesecond population of particulate microencapsulated acetamide herbicidehas a mean particle size of from about 11.5 μm to about 14 μm.